WO2024101172A1 - Composé d'urée (hétéro)aryle et insecticide - Google Patents

Composé d'urée (hétéro)aryle et insecticide Download PDF

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Publication number
WO2024101172A1
WO2024101172A1 PCT/JP2023/038749 JP2023038749W WO2024101172A1 WO 2024101172 A1 WO2024101172 A1 WO 2024101172A1 JP 2023038749 W JP2023038749 W JP 2023038749W WO 2024101172 A1 WO2024101172 A1 WO 2024101172A1
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Prior art keywords
group
added
trifluoromethyl
compound
triazol
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PCT/JP2023/038749
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English (en)
Japanese (ja)
Inventor
史也 西尾
聖 牧野
衆一 伊藤
理奈 矢田
昌宏 川口
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日本曹達株式会社
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Publication of WO2024101172A1 publication Critical patent/WO2024101172A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/04—Insecticides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to a (hetero)aryl urea compound and an insecticide. More specifically, the present invention relates to a (hetero)aryl urea compound that has excellent insecticidal activity, is safe, and can be synthesized industrially advantageously, and to an insecticide containing the same as an active ingredient.
  • This application claims priority based on Japanese Patent Application No. 2022-180255, filed on November 10, 2022, the contents of which are incorporated herein by reference.
  • Patent Document 1 teaches that the compound represented by formula (P1) can be used as an insecticide.
  • the object of the present invention is to provide a (hetero)aryl urea compound that has excellent insecticidal activity, is safe, and can be synthesized industrially in an advantageous manner, and an insecticide that contains the compound as an active ingredient.
  • a 1 represents a nitrogen atom or a group represented by CH;
  • R 1 represents a C1-6 haloalkoxy group or a C1-6 haloalkylthio group;
  • R a represents a hydrogen atom or a substituted or unsubstituted C3-6 cycloalkyl group;
  • B1 represents a nitrogen atom or a group represented by CH;
  • B2 represents a nitrogen atom or a group represented by CXb ;
  • Xa and Xb each independently represent a hydrogen atom, a halogeno group, a C1-6 haloalkoxy group, a carbamoyl group, a thiocarbamoyl group, or a cyano group.
  • An insecticide comprising at least one compound or a salt thereof according to [1] as an active ingredient.
  • the (hetero)aryl urea compound of the present invention has excellent insecticidal activity, is safe, and can be synthesized industrially advantageously.
  • the insecticide of the present invention can effectively control agricultural pests at low concentrations.
  • the first embodiment of the present invention is a compound represented by formula (I) (hereinafter, sometimes referred to as compound (I)) or a salt thereof. (Hereinafter, compound (I) or a salt thereof may be referred to as a (hetero)aryl urea compound.)
  • the term "unsubstituted” means that only the group serving as the mother nucleus is present. When the term “substituted” is not used and only the name of the group serving as the mother nucleus is used, it means “unsubstituted” unless otherwise specified.
  • the term “substituted” means that any hydrogen atom of the core group is replaced with a group (substituent) having the same or different structure as the core group. Therefore, a “substituent” is another group bonded to the core group.
  • the number of substituents may be one or more.
  • the two or more substituents may be the same or different.
  • C1-6 indicates that the number of carbon atoms in the core group is 1 to 6. This number of carbon atoms does not include the number of carbon atoms in the substituent.
  • a butyl group having an ethoxy group as a substituent is classified as a C2 alkoxy C4 alkyl group.
  • the "substituent” is not particularly limited as long as it is chemically permissible and has the effect of the present invention. Examples of groups that can be the “substituent” are shown below. C1-6 alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, or an n-hexyl group; C2-6 alkenyl groups such as a vinyl group, a 1-propenyl group, a 2-propenyl group (allyl group), a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-methyl-2-propenyl group, and a 2-methyl-2-propenyl group; C2-6 alkynyl groups such as an ethyny
  • C3-6 cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; C6-10 aryl groups such as phenyl groups and naphthyl groups; C6-10 aryl C1-6 alkyl groups such as a benzyl group and a phenethyl group; 3- to 6-membered heterocyclyl groups; 3-6 membered heterocyclyl C1-6 alkyl group;
  • C1-6 alkoxy groups such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an s-butoxy group, an i-butoxy group, or a t-butoxy group
  • C2-6 alkenyloxy groups such as a vinyloxy group, an allyloxy group, a propenyloxy group, or a butenyloxy group
  • C2-6 alkynyloxy groups such as ethynyloxy groups, propargyloxy groups, etc.
  • C6-10 aryloxy groups such as a phenoxy group and a naphthoxy group
  • C6-10 aryl C1-6 alkoxy groups such as a benzyloxy group and a phenethyloxy group
  • 5- to 6-membered heteroaryloxy groups such as thiazolyloxy groups and pyridyloxy groups
  • Formyl group C1-6 alkylcarbonyl groups such as acetyl group and propionyl group; Formyloxy group; C1-6 alkylcarbonyloxy groups such as an acetyloxy group or a propionyloxy group; C6-10 arylcarbonyl groups such as a benzoyl group; C1-6 alkoxycarbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, or a t-butoxycarbonyl group; C1-6 alkoxycarbonyloxy groups such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, an i-propoxycarbonyloxy group, an n-butoxycarbonyloxy group, or a t-butoxycarbonyloxy group; Carboxyl group;
  • halogeno groups such as a fluoro group, a chloro group, a bromo group, or an iodo group
  • C1-6 haloalkyl groups such as a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a 3,3,3-trifluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a perfluoropropyl group, a 2,2,2-trifluoro-1-trifluoromethylethyl group, a perfluoroisopropyl group, a 4-fluorobutyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a chloromethyl group
  • Amino group C1-6 alkyl-substituted amino groups such as methylamino group, dimethylamino group, and diethylamino group; C6-10 arylamino groups such as anilino group and naphthylamino group; C6-10 aryl C1-6 alkylamino groups such as a benzylamino group or a phenethylamino group; Formylamino group; C1-6 alkylcarbonylamino groups such as an acetylamino group, a propanoylamino group, a butyrylamino group, or an i-propylcarbonylamino group; C1-6 alkoxycarbonylamino groups such as a methoxycarbonylamino group, an ethoxycarbonylamino group, an n-propoxycarbonylamino group, or an i-propoxycarbonylamino group; unsubstituted or substituted aminocarbonyl groups, such as an
  • C1-6 alkylthio groups such as a methylthio group, an ethylthio group, an n-propylthio group, an i-propylthio group, an n-butylthio group, an i-butylthio group, an s-butylthio group, or a t-butylthio group
  • C1-6 haloalkylthio groups such as a trifluoromethylthio group, a 2,2,2-trifluoroethylthio group, etc.
  • C6-10 arylthio groups such as a phenylthio group and a naphthylthio group
  • 5- to 6-membered heteroarylthio groups such as thiazolylthio groups and pyridylthio groups
  • C1-6 alkylthio groups such as a methylthio group, an ethylthio group, an n-propylthio group, an i-propy
  • C1-6 alkylsulfinyl groups such as a methylsulfinyl group, an ethylsulfinyl group, or a t-butylsulfinyl group; C1-6 haloalkylsulfinyl groups such as a trifluoromethylsulfinyl group or a 2,2,2-trifluoroethylsulfinyl group; C6-10 arylsulfinyl groups such as a phenylsulfinyl group; 5- to 6-membered heteroarylsulfinyl groups such as thiazolylsulfinyl groups and pyridylsulfinyl groups;
  • C1-6 alkylsulfonyl groups such as a methylsulfonyl group, an ethylsulfonyl group, or a t-butylsulfonyl group; C1-6 haloalkylsulfonyl groups such as a trifluoromethylsulfonyl group or a 2,2,2-trifluoroethylsulfonyl group; C6-10 arylsulfonyl groups such as a phenylsulfonyl group; 5- to 6-membered heteroarylsulfonyl groups such as thiazolylsulfonyl groups and pyridylsulfonyl groups; C1-6 alkylsulfonyloxy groups such as a methylsulfonyloxy group, an ethylsulfonyloxy group, or a t-butylsulfonyloxy group; C1-6 haloalkyls
  • triC1-6 alkyl-substituted silyl groups such as a trimethylsilyl group, a triethylsilyl group, or a t-butyldimethylsilyl group; triC6-10 aryl-substituted silyl groups such as triphenylsilyl groups; Cyano group; Nitro group.
  • any of the hydrogen atoms in these "substituents” may be replaced with a group of a different structure.
  • examples of the "substituents” include a C1-6 alkyl group, a C1-6 haloalkyl group, a C1-6 alkoxy group, a C1-6 haloalkoxy group, a halogeno group, a cyano group, and a nitro group.
  • the above “3- to 6-membered heterocyclyl group” contains 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur atoms as ring-constituting atoms.
  • Examples of the “3- to 6-membered heterocyclyl group” include 3- to 6-membered saturated heterocyclyl groups, 5- to 6-membered partially unsaturated heterocyclyl groups, and 5- to 6-membered heteroaryl groups.
  • Examples of the 3- to 6-membered saturated heterocyclyl group include an aziridinyl group, an epoxy group, a pyrrolidinyl group, a tetrahydrofuranyl group, a thiazolidinyl group, a piperidyl group, a piperazinyl group, a morpholinyl group, a dioxolanyl group, and a dioxanyl group.
  • Examples of the 5-membered partially unsaturated heterocyclyl group include a pyrrolinyl group, a dihydrofuranyl group, an imidazolinyl group, a pyrazolinyl group, an oxazolinyl group, and an isoxazolinyl group.
  • Examples of the six-membered partially unsaturated heterocyclyl group include a dihydropyranyl group.
  • Examples of the 5-membered heteroaryl group include a pyrrolyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a triazolyl group, an oxadiazolyl group, a thiadiazolyl group, and a tetrazolyl group.
  • 6-membered heteroaryl group examples include a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, and a triazinyl group.
  • a 1 represents a nitrogen atom or a group represented by CH.
  • R 1 represents a C1-6 haloalkoxy group or a C1-6 haloalkylthio group.
  • C1-6 haloalkoxy group include a difluoromethoxy group, a trifluoromethoxy group; a 2,2-difluoroethoxy group, a 2,2,2-trifluoroethoxy group, a 1,1,2,2-tetrafluoroethoxy group, a pentafluoroethoxy group; a 3,3-difluoropropoxy group, a 3,3,3-trifluoropropoxy group, a 2,2,3,3,3-pentafluoropropoxy group, a 1,2,2,3,3,3-hexafluoropropoxy group, a perfluoropropoxy group; a 2,2,2-trifluoro-1-trifluoromethylethoxy group, a perfluoroisopropoxy group; a 2,2,3,3,4,4,4-heptafluoro
  • C1-6 haloalkylthio group includes difluoromethylthio group, trifluoromethylthio group, 2,2-difluoroethylthio group, 2,2,2-trifluoroethylthio group, 1,1,2,2-tetrafluoroethylthio group, pentafluoroethylthio group, 3,3-difluoropropylthio group, 3,3,3-trifluoropropylthio group, 2,2,3,3,3-pentafluoropropylthio group, 1,2,2,3,3,3-hexafluoropropylthio group, perfluoropropylthio group, 2,2,2-trifluoro-1-trifluoromethylethylthio group, perfluoroisopropylthio group, 2,2,3,3,4,4,4-heptafluorobutylthio group, 1,2,2,3,3,4,4,4-octafluoropropylthio group, Examples include
  • R1 is preferably a C1-2 fluoroalkoxy group such as a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, a 2,2,2-trifluoroethoxy group, a 1,1,2,2-tetrafluoroethoxy group, or a pentafluoroethoxy group; or a C1-2 fluoroalkylthio group such as a difluoromethylthio group, a trifluoromethylthio group, a 2,2-difluoroethylthio group, a 2,2,2-trifluoroethylthio group, a 1,1,2,2-tetrafluoroethylthio group, or a pentafluoroethylthio group.
  • R 1 is preferably a 2,2,2-trifluoroethoxy group, a 1,1,2,2-tetrafluoroethoxy group, or a trifluoromethylthio
  • R a represents a hydrogen atom, or a substituted or unsubstituted C3-6 cycloalkyl group.
  • C3-6 cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
  • Preferred substituents on a "C3 to 6 cycloalkyl group” are: a halogeno group such as a fluoro group, a chloro group, a bromo group or an iodo group; a hydroxyl group; a C1 to 6 alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an s-butoxy group, an i-butoxy group or a t-butoxy group; a C1 to 6 haloalkoxy group such as a 2-chloro-n-propoxy group, a 2,3-dichlorobutoxy group or a trifluoromethoxy group; a phenyl group; a "phenyl group substituted with a halogeno group, a C1 to 6 haloalkyl group or a C1 to 6 haloalkoxy group” such as a 4-chlor
  • B 1 represents a nitrogen atom or a group represented by CH
  • B 2 represents a nitrogen atom or a group represented by CX b .
  • Xa and Xb each independently represent a hydrogen atom, a halogeno group, a C1-6 haloalkoxy group, a carbamoyl group, a thiocarbamoyl group, or a cyano group.
  • halogeno group include a fluoro group, a chloro group, a bromo group, and an iodo group.
  • C1-6 haloalkoxy group include the same groups as those exemplified for R1 .
  • the salt of compound (I) in this embodiment is not particularly limited as long as it is an agriculturally and horticulturally acceptable salt.
  • Examples of salts of compound (I) include salts of inorganic acids such as hydrochloric acid and sulfuric acid; salts of organic acids such as acetic acid and lactic acid; salts of alkali metals such as lithium, sodium, and potassium; salts of alkaline earth metals such as calcium and magnesium; salts of transition metals such as iron and copper; salts of ammonia; and salts of organic bases such as triethylamine, tributylamine, pyridine, and hydrazine.
  • the method for producing the compound (I) of the present embodiment is not particularly limited.
  • the compound (I) can be obtained by a production method utilizing a known reaction described in the Examples, etc.
  • it can be obtained by the production method described in Patent Document 1.
  • the salt of compound (I) can be obtained from compound (I) by a known method.
  • Compound (I) of the present embodiment can be obtained, for example, by utilizing a reaction as shown in the reaction scheme below.
  • Reaction Scheme 1 Compound (I) can be obtained by reacting a compound represented by formula (I-1) with a compound represented by formula (I-2). This reaction can be carried out in the presence of a base or a catalyst.
  • the second embodiment of the present invention is an insecticide containing at least one selected from the compound (I) of the first embodiment or a salt thereof as an active ingredient.
  • the amount of the (hetero)aryl urea compound contained in the insecticide of this embodiment is not particularly limited as long as it shows an insecticidal effect.
  • the (hetero)aryl urea compound of the present embodiment is a highly safe substance because it has little phytotoxicity to crops and low toxicity to fish and warm-blooded animals, and is therefore useful as an active ingredient of insecticides.
  • the (hetero)aryl urea compound of the present embodiment exhibits excellent control effects not only against susceptible pests, but also against various resistant pests.
  • the (hetero)aryl urea compound of the present embodiment (hereinafter, sometimes referred to as the compound of the present invention) is effective against all developmental stages of organisms to be controlled, and exhibits excellent control effects against, for example, eggs, nymphs, larvae, pupae, and adults of mites, insects, and the like.
  • the insecticide of the second embodiment is preferably used on plants such as grains, vegetables, root vegetables, potatoes, flowers, fruit trees, ornamental plants, trees such as tea, coffee, and cacao, pasture grasses, turf grasses, and cotton.
  • the insecticide may be applied to any part of the plant, such as leaves, stems, stalks, flowers, buds, fruits, seeds, sprouts, roots, tubers, tuberous roots, shoots, cuttings, etc.
  • the insecticide is not particularly limited by the species of the plant to which it is applied, and examples of the species of the plant include original species, varieties, improved varieties, cultivated varieties, mutants, hybrids, genetically modified organisms (GMOs), and the like.
  • the above insecticides can be used for controlling various agricultural pests by seed treatment, foliage spray, soil application, water surface application, and the like.
  • Butterflies or moths of the order Lepidoptera (a) Arctiidae moths, such as Hyphantria cunea and Lemyra imparilis; (b) Bucculatricidae moths, for example, Bucculatrix pyrivorella; (c) moths of the family Carposinidae, for example, the peach fruit moth (Carposina sasakii); (d) Crambidae moths, for example, Diaphania spp., Diaphania indica, Diaphania nitidalis; for example, Ostrinia spp., Ostrinia furnacalis, Ostrinia nubilalis, Ostrinia scapulalis; others, Chilo suppressalis, Cnaphalocrocis medinalis, Conogethes punct
  • Heliothis spp. for example, Heliothis armigera, Heliothis virescens; others, for example, Aedia leucomelas, Ctenoplusia agnata, Eudocima tyrannus, Mamestra brassicae, Mythimna separata, Naranga aenescens, Panolis japonica, Peridroma saucia, Pseudoplusia includens, Trichoplusia ni); (m) Nolidae moths, for example, Earias insulana; (n) Butterflies of the family Pieridae, for example, Pieris spp., Pieris brassicae, Pieris rapae crucivora; (O) Plutellidae moths, for example, Acrolepiopsis spp., such as Acrolepiopsis sapporensis and Acrolepiopsis suzukiella; others, such as Plutella x
  • Thysanoptera pests (a) Phlaeothripidae, for example, Ponticulothrips diospyrosi; (b) Thripidae, for example, Frankliniella spp., Frankliniella intonsa, Frankliniella occidentalis; Thrips spp., Thrips palmi, Thrips tabaci; and others, Heliothrips haemorrhoidalis, Scirtothrips dorsalis.
  • Phlaeothripidae for example, Ponticulothrips diospyrosi
  • Thripidae for example, Frankliniella spp., Frankliniella intonsa, Frankliniella occidentalis
  • Thrips spp. Thrips palmi, Thrips tabaci
  • Heliothrips haemorrhoidalis Scirtothrips dorsalis.
  • Cicadellidae for example, Empoasca spp., potato leafhopper (Empoasca fabae), persimmon leafhopper (Empoasca nipponica), tea green leafhopper (Empoasca onukii), bean green leafhopper (Empoasca sakaii); other, Arboridia apicalis, Balclutha saltuella, Epiacanthus stramineus, Macrosteles striifrons, Nephotettix cinctinceps.
  • Empoasca spp. potato leafhopper (Empoasca fabae), persimmon leafhopper (Empoasca nipponica), tea green leafhopper (Empoasca onukii), bean green leafhopper (Empoasca sakaii); other, Arboridia apicalis, Balclutha saltuella, Epiacanthus stramineus, Macrosteles striifrons, Nephotettix cinctinceps.
  • C Heteroptera
  • Alydidae for example, Riptortus clavatus
  • Coreidae for example, Cletus punctiger, Leptocorisa chinensis
  • Lygaeidae for example, Blissus leucopterus, Cavelerius saccharivorus, Togo hemipterus
  • Miridae for example, Halticus insularis, Lygus lineolaris, Psuedatomoscelis seriatus, Stenodema sibiricum, Stenotus rubrovittatus, Trigonotylus caelestialium
  • Miridae for example, Halticus insularis, Lygus lineolaris, Psuedatomoscelis seriatus, Stenodema sibiricum, Stenotus rubrovittatus, Trigonotylus caelestialium
  • Pentatomidae for example, Nezara spp., Nezara antennata, Nezara viridula; for example, Eysarcoris spp., Eysarcoris aeneus, Eysarcoris lewisi, Eysarcoris ventralis, Dolycoris baccarum, Eurydema rugosum, Glaucias subpunctatus, Halyomorpha halys, Piezodorus hybneri), Plautia crossota, Scotinophora lurida;
  • Pyrrhocoridae for example, Dysdercus cingulatus;
  • Rhopalidae for example, Rhopalus msculatus;
  • Scutelleridae for example, Eurygaster integriceps;
  • Tingidae for example, Stephanitis nashi.
  • (D) Sternorrhyncha (a) Adelgidae, for example, Adelges laricis; (b) Aleyrodidae, for example, Bemisia spp., silverleaf whitefly (Bemisia argentifolii), tobacco whitefly (Bemisia tabaci); other, Aleurocanthus spiniferus, Dialeurodes citri, Trialeurodes vaporariorum; (c) Aphididae, for example, Aphis spp., bean aphid (Aphis craccivora), bean black aphid (Aphis fabae), strawberry aphid (Aphis forbesi), cotton aphid (Aphis gossypii), European apple aphid (Aphis pomi), elder aphid (Aphis sambuci), Yukiyanagi aphid (Aphis spiraecola); for example, Rhopalosiphum s
  • Pests of the suborder Polyphaga (a) of the family Anobiidae, for example, the cigarette beetle (Lasioderma serricorne); (b) Attelabidae, for example, Byctiscus betulae, Rhynchites heros; (C) Bostrichidae, for example, Lyctus brunneus; (d) Brentidae, for example, Cylas formicarius; (e) Buprestidae, for example, Agrilus sinuatus; (F) Cerambycidae, for example, Anoplophora malasiaca, Monochamus alternatus, Psacothea hilaris, Xylotrechus pyrrhoderus; (g) Chrysomelidae, for example, Bruchus spp., pea weevil (Bruchus pisorum), broad bean weevil (Bruchus rufimanus); for example, Diabrotica spp., northern
  • Curculionidae for example, Anthonomus spp., such as Anthonomus grandis and Anthonomus pomor
  • Pests of the order Diptera (A) Suborder Brachycera (a) Agromyzidae, for example, Liriomyza spp., Liriomyza bryoniae, Liriomyza chinensis, Liriomyza sativae, Liriomyza trifolii; others, Chromatomyia horticola, Agromyza oryzae; (b) Anthomyiidae, for example, Delia spp., such as Delia platura and Delia radicum; and others, such as Pegomya cunicularia; (C) Drosophilidae, for example, Drosophila spp., Drosophila melanogaster, Drosophila suzukii; (D) Ephydridae, for example, Hydrellia griseola; (e) from the family Psilidae, for example, the carrot fly (Psila rosae); (F) Teph
  • Nematocera (A) Cecidomyiidae, for example, Asphondylia yushimai, Contarinia sorghicola, Mayetiola destructor, and Sitodiplosis mosellana.
  • Orthoptera pests for example, Schistocerca spp., American locust (Schistocerca americana), desert locust (Schistocerca gregaria); other, Australian locust (Chortoicetes terminifera),ixie locust (Dociostaurus maroccanus), migratory locust (Locusta migratoria), brown locust (Locustana pardalina), red locust (Nomadacris septemfasciata), Oxya yezoensis; (b) from the family Gryllidae, for example, the European house cricket (Acheta domestica), the field cricket (Teleogryllus emma); (c) Gryllotalpidae, for example, Gryllotalpa orientalis; (d) From the family Tettigoniidae, for example, Tachycines asynamorus.
  • Acrididae for example, Schistocerca spp., American locust
  • the insecticide of the second embodiment of the present invention may be mixed or used in combination with other active ingredients such as fungicides, insecticides/acaricides, nematicides, and soil pesticides; plant regulators, synergists, fertilizers, soil conditioners, and animal feed.
  • active ingredients such as fungicides, insecticides/acaricides, nematicides, and soil pesticides; plant regulators, synergists, fertilizers, soil conditioners, and animal feed.
  • the combination of the compound of the present invention and other active ingredients is expected to have a synergistic effect in terms of insecticidal, acaricidal and nematocidal activities.
  • the synergistic effect can be confirmed by Colby's formula (Colby.SR; Calculating Synergistic and Antagonistic Responses of Herbicide Combinations; Weeds 15, 20-22, 1967) in accordance with a conventional method.
  • insecticides examples include acaricides, nematicides, soil pesticides, etc. that can be mixed or used in combination with the insecticide of the present invention are shown below. The following list is based on the IRAC insecticide mode of action classification table.
  • Acetylcholinesterase (AChE) inhibitors (carbamate type) Alanycarb, Aldicarb, Bendiocarb, Benfuracarb, Butocarboxim, Butoxycarboxim, Carbaryl, Carbofuran, Carbosulfan, Ethiofencarb, Fenobucarb, Formetanate, Furathiocarb, Isoprocarb, Methiocarb, Methomyl, Metolcarb, Oxamyl, Piricarb micarb, Propoxur, Thiodicarb, Thiofanox, Triazamate, Trimethacarb, XMC, Xylylcarb; Aldoxycarb, Allyxycarb, Aminocarb, Bufencarb, Cloethocarb, Fenothiocarb, Promecarb.
  • AChE Acetylcholinesterase
  • Acetylcholinesterase (AChE) inhibitors organophosphorus (organophosphorus) Acephate, Azamethiphos, Azinphos-ethyl, Azinphosmethyl, Cadusafos, Chlorethoxyfos, Chlorfenvinphos, Chlormephos, Chlorpyrifos, Chlorpyrifos-methyl, Coumaphos, Cyanophos, Demeton-S-methyl, Diazinon, Dichlorvos DDVP), Dicrotophos, Dimethoate, Dimethylvinphos, Disulfoton, EPN, Ethion, Ethoprophos, Famphur, Fenamiphos, Fenitrothion, Fenthion, Fosthiazate, Heptenophos, Imicyafos, Isofenphos, Isopropyl O-(methoxyaminothio-phosphoryl) salicylate salicylate, Isoxathion, Malathion, Mecarb
  • chloride ion channel blockers Chlordane, Endosulfan; Ethiprole, Fipronil; Acetoprole, Camphechlor, Dienochlor, Heptachlor, Pyrafluprole, Pyriprole; Flufiprole.
  • Nicotinic acetylcholine receptor (nAChR) competitive modulators Acetamiprid, Clothianidin, Dinotefuran, Imidacloprid, Nitenpyram, Thiacloprid, Thiamethoxam; Nicotine; Sulfoxaflor; Flupyradifurone; Triflumezopyrim; Nithiazine, Dichloromezotiaz, Flupyrimin.
  • Glutamate-gated chloride ion (chloride ion) channel (GluCl) allosteric modulators Abamectin, Emamectin, Emamectin-benzoate, Lepimectin, Milbemectin; Doramectin, Eprinomectin, Ivermectin, Moxidectin, Selamectin.
  • Chitin biosynthesis inhibitor type 0 Bistrifluron, Chlorfluazuron, Diflubenzuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, Novaluron, Noviflumuron, Teflubenzuron, Triflumuron; Fluazuron.
  • Chitin biosynthesis inhibitor type 1 Buprofezin.
  • Molting inhibitor Cyromazine.
  • Mitochondrial electron transport chain complex IV inhibitors Aluminum phosphide (Al-phosphide), calcium phosphide (Ca-phosphide), zinc phosphide (Zn-phosphide), phosphine (Phosphine); calcium cyanide (Ca-cyanide), sodium cyanide (Na-cyanide), potassium cyanide (K-cyanide).
  • mitochondrial electron transport chain complex II inhibitors Cyenopyrafen, Cyflumetofen; Pyflubumide.
  • Baculovirus granulosis viruses (Cydia pomonella GV, Thaumatotibia leucotreta GV) Nuclear polyhedrosis viruses (Anticarsia gemmatalis MNPV, Heliocoverpa armigera NPV).
  • KCa2 Calcium-activated potassium channel
  • 32) Mitochondrial electron transport complex III inhibitor (Qi site) Flometoquin.
  • Chordotonal organ modulator (target site unspecified) Dimpropyridaz.
  • anthelmintics that can be mixed or used in combination with the insecticide of the present invention are shown below.
  • Benzimidazoles fenbendazole, albendazole, triclabendazole, oxibendazole, mebendazole, oxfendazole, perbendazole, flubendazole, febantel, netobimin, thiophanate, thiabendazole, and cambendazole.
  • Salicylanilides closantel, oxyclozanide, rafoxanide, niclosamide.
  • Substituted phenols nitroxynil, nitrosulfonate.
  • Pyrimidines pyrantel, morantel.
  • Imidazothiazoles levamisole, tetramisole.
  • Tetrahydropyrimidines praziquantel, epsiprantel.
  • Other anthelmintics cyclodiene, ryania, clorsulon, metronidazole, demiditraz, piperazine, diethylcarbamazine, dichlorophene, monepantel, tribendimidine, amidantel, thiacetarsamide, melarsomine, and arsenamide.
  • Nucleic acid synthesis metabolic inhibitors (1) RNA polymerase I inhibitors Benalaxyl, Benalaxyl M, Furalaxyl, Metalaxyl, Metalaxyl M; Oxadixyl; Ofurace. (2) Adenosine deaminase inhibitors: bupirimate, dimethirimol, ethirimol. (3) DNA/RNA biosynthesis inhibitors: hymexazole, octhilinone. (4) DNA topoisomerase type II inhibitor oxolinic acid. (5) DHODH inhibitors: ipflufenoquine, quinofumelin.
  • Inhibitors of cytoskeleton and motor proteins (1) ⁇ -tubulin polymerization inhibitors: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate, thiophanate-methyl, diethofencarb, zoxamide, ethaboxam. (2) Other inhibitors: Pencycuron, fluopicolide, fenamacryl, metrafenone, pyriophenone, pyridaclomethyl.
  • Inhibitors of sterol biosynthesis in cell membranes (1) Inhibitors of C14 demethylase (erg11/cyp51) in sterol biosynthesis Triforine; pyrifenox, pyrisoxazole; fenarimol, nuarimol; imazalil, oxpoconazole, pefurazoate, prochloraz, triflumizole; azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, mefentrifluconazole, metconazole, myclobutanil, penconazole, propiconazole, simeconazole, tebuconazole
  • Inhibitors of cell wall melanin synthesis Fthalide; pyroquilon; tricyclazole. Carpropamid, diclocymet, fenoxanil. Tolprocarb.
  • (L) Agents exhibiting multisite contact activity Copper (various salts), basic copper sulfate, Bordeaux mixture, copper hydroxide, copper naphthalate, copper oxychloride, copper sulfate, copper oxide, copper oxine; sulfur, lime sulfur mixture; ferbam, mancozeb, maneb, metiram, propineb, thiuram, zinc thiazole, zineb, ziram; captan, captafol, folpet; chlorothalonil; dichlofluanid, tolylfluanid; guazatine, guazatine acetate, iminoctadine, iminoctadine acetate, iminoctadine albesilate; anilazine; dithianone; quinomethionate; fluoroimide; metasulfocarb.
  • plant regulators that can be mixed or used in combination with the insecticide of the present invention are shown below.
  • Formulation The formulations of the insecticide of the present invention are shown below, but the additives and the ratio of addition should not be limited to these examples and can be changed in a wide range. In the formulations, parts indicate parts by mass, and % indicates % by mass. The formulations for agricultural and horticultural use and for paddy rice are shown below.
  • Formulation 4 Granules 5 parts of the compound of the present invention, 73 parts of clay, 20 parts of bentonite, 1 part of dioctyl sulfosuccinate sodium salt, and 1 part of potassium phosphate are thoroughly ground and mixed, water is added, the mixture is thoroughly kneaded, and then granulated and dried to obtain granules containing 5% of the active ingredient.
  • Formulation 5 Suspension 10 parts of the compound of the present invention, 4 parts of polyoxyethylene alkyl allyl ether, 2 parts of sodium polycarboxylate, 10 parts of glycerin, 0.2 parts of xanthan gum, and 73.8 parts of water are mixed and wet-pulverized until the particle size becomes 3 microns or less, to obtain a suspension containing 10% of the active ingredient.
  • TEA triethylamine.
  • DMF N,N-dimethylformamide.
  • THF tetrahydrofuran.
  • DIPEA diisopropylethylamine.
  • DMAP 4-dimethylaminopyridine.
  • TMEDA tetramethylethylenediamine.
  • Boc2O di-tert-butyl dicarbonate.
  • tBuXPhos 2-di-tert-butylphosphino-2',4',6'-triisopropylbiphenyl.
  • Pd2(dba)3 tris(dibenzylideneacetone)dipalladium(0).
  • Pd(PPh3)4 tetrakis(triphenylphosphine)palladium(0).
  • tert-butyl [1-[ ⁇ (dimethylamino)methylene ⁇ amino]-1-oxopropan-2-yl]carbamate (12.9 g) was dissolved in 1,4-dioxane (180 ml) and acetic acid (89 ml), and 2-hydrazineylpyrimidine (7.0 g) was added thereto and stirred at 60° C. for 4 hours. The reaction mixture was then evaporated under reduced pressure, and the resulting concentrate was purified by silica gel column chromatography to obtain the target compound (11.0 g) in a yield of 71%.
  • Trifluoroethanol (0.6 g) was dissolved in DMF (4 ml) and cooled to 0° C. Sodium hydride (0.24 g) was then added and the mixture was stirred at 0° C. for 30 minutes. Thereafter, 2-fluoro-1-nitro-4-(trifluoromethyl)benzene (0.84 g) was added and the mixture was further stirred at room temperature overnight. Water was then added to the reaction solution, which was then extracted with ethyl acetate and washed with saturated saline, and the organic layer was dried over anhydrous magnesium sulfate. The solvent was then distilled off under reduced pressure, and the resulting concentrate was purified by silica gel column chromatography to obtain the target compound (1.23 g).
  • 2-(2,2,2-trifluoroethoxy)-4-(trifluoromethyl)aniline (0.22 g) was dissolved in THF (4 ml) and cooled to 0° C. Then, TEA (0.36 ml) and triphosgene (0.1 g) were added in that order and stirred at 0° C. for 30 minutes. Then, 1- ⁇ 1-(pyrimidin-2-yl)-1H-1,2,4-triazol-5-yl ⁇ ethan-1-aminedihydrochloride (0.22 g) and TEA (0.36 ml) were added and the mixture was further stirred at room temperature for 2 hours.
  • 6-(trifluoromethyl)pyridin-3-amine (17.6 g) was dissolved in dichloromethane (270 ml), and DIPEA (22.8 ml), DMAP (1.33 g), and pivaloyl chloride (14.7 ml) were added successively, and the mixture was stirred at room temperature overnight.
  • the reaction mixture was then mixed with a saturated aqueous solution of sodium bicarbonate, extracted with dichloromethane, washed with saturated saline, and the organic layer was dried over anhydrous magnesium sulfate.
  • the solvent was then distilled off under reduced pressure, and the resulting crystals were washed with diethyl ether to obtain the target compound (13.93 g). Yield: 52%.
  • N-(6-(trifluoromethyl)pyridin-3-yl)pivalamide (4.26 g) was dissolved in THF (58 ml), TMEDA (6.4 ml) was added, and the mixture was cooled to ⁇ 78° C. Then, a 2.64 M nBuLi hexane solution (16 ml) was added dropwise, and the mixture was further stirred at ⁇ 78° C. for 1 hour. Thereafter, a solution of iodine (5.3 g) in THF (35 ml) was added, the temperature was raised to 0° C., and the mixture was further stirred for 1 hour.
  • N-(6-(trifluoromethyl)-4-((trifluoromethyl)thio)pyridin-3-yl)pivalamide (0.59 g) was dissolved in concentrated sulfuric acid (5.6 ml) and stirred at 100° C. for 1 hour. The reaction mixture was then added to a saturated aqueous solution of sodium carbonate, extracted with ethyl acetate, washed with saturated saline, and the organic layer was dried over anhydrous magnesium sulfate. The solvent was then distilled off under reduced pressure to obtain the target compound (0.44 g). Yield: 100%.
  • 6-(trifluoromethyl)-4-((trifluoromethyl)thio)pyridin-3-amine (0.1 g) was dissolved in THF (1.9 ml) and cooled to 0° C. Then, TEA (0.16 ml) and triphosgene (45 mg) were added in that order and stirred at 0° C. for 30 minutes. Then, 1- ⁇ 1-(pyrimidin-2-yl)-1H-1,2,4-triazol-5-yl ⁇ ethan-1-amine dihydrochloride (0.11 g) and TEA (0.16 ml) were added and the mixture was further stirred at room temperature for 4 hours.
  • 6-(trifluoromethyl)-4-((trifluoromethyl)thio)pyridin-3-amine 80 mg was dissolved in THF (1.6 ml) and cooled to 0° C. Then, TEA (0.13 ml) and triphosgene (36 mg) were added in that order and stirred at 0° C. for 30 minutes. Then, 1-(1-(5-fluoropyrimidin-2-yl)-1H-1,2,4-triazol-5-yl)ethan-1-amine (75 mg) and TEA (0.13 ml) were added and the mixture was further stirred at room temperature for 2 hours.
  • tert-butyl [1-[ ⁇ (dimethylamino)methylene ⁇ amino]-1-oxopropan-2-yl]carbamate (2.3 g) was dissolved in 1,4-dioxane (31 ml) and acetic acid (16 ml), and 5-fluoro-2-hydrazineylpyridine (1.45 g) was added thereto and stirred at 60° C. for 4 hours. The reaction mixture was then evaporated under reduced pressure, and the resulting concentrate was purified by silica gel column chromatography to obtain the target compound (1.9 g) in a yield of 66%.
  • tert-butyl (1-(1-(5-fluoropyridin-2-yl)-1H-1,2,4-triazol-5-yl)ethyl)carbamate (1.9 g) was dissolved in dichloromethane (40 ml), and a 4M solution of hydrochloric acid in 1,4-dioxane (8 ml) was added thereto, followed by stirring at room temperature overnight. The reaction mixture was then evaporated under reduced pressure to give crystals which were then used in the next step.
  • 6-(trifluoromethyl)-4-((trifluoromethyl)thio)pyridin-3-amine (0.1 g) was dissolved in THF (1.9 ml) and cooled to 0° C. Then, TEA (0.16 ml) and triphosgene (45 mg) were added in that order and stirred at 0° C. for 30 minutes. Then, 1-(1-(5-fluoropyridin-2-yl)-1H-1,2,4-triazol-5-yl)ethan-1-amine hydrochloride (93 mg) and TEA (0.16 ml) were added and the mixture was further stirred at room temperature for 4 hours.
  • tert-butyl [1-[ ⁇ (dimethylamino)methylene ⁇ amino]-1-oxopropan-2-yl]carbamate (18.5 g) was dissolved in 1,4-dioxane (250 ml) and acetic acid (130 ml), and 6-hydrazineylnicotinonitrile (12.2 g) was added thereto, followed by stirring at 60° C. for 4 hours. The reaction mixture was then evaporated under reduced pressure, and the resulting concentrate was purified by silica gel column chromatography to obtain the target compound (4.52 g) in a yield of 19%.
  • tert-butyl (1-(1-(5-cyanopyridin-2-yl)-1H-1,2,4-triazol-5-yl) ethyl) carbamate (1.93 g) was dissolved in dichloromethane (41 ml), and a 4M solution of hydrochloric acid in 1,4-dioxane (8 ml) was added thereto, followed by stirring at room temperature overnight. The reaction mixture was then evaporated under reduced pressure to give crystals which were then used in the next step.
  • 6-(trifluoromethyl)-4-((trifluoromethyl)thio)pyridin-3-amine (0.1 g) was dissolved in THF (1.9 ml) and cooled to 0° C. Then, TEA (0.16 ml) and triphosgene (45 mg) were added in that order and stirred at 0° C. for 30 minutes. Thereafter, 6-(5-(1-aminoethyl)-1H-1,2,4-triazol-1-yl)nicotinonitrile hydrochloride (96 mg) and TEA (0.16 ml) were added and the mixture was further stirred at room temperature for 4 hours.
  • 2-(1,3-dioxoisoindolin-2-yl)propanoic acid (5.4 g) was dissolved in dichloromethane (82 ml) and cooled to 0° C. Then, oxalyl chloride (4.2 ml) and a catalytic amount of DMF were added and stirred at room temperature for 1 hour. The solvent was then distilled off under reduced pressure to obtain the acid chloride. Next, ethyl cyclopropanecarbimidate hydrochloride (3.69 g) was dissolved in THF (82 ml) and cooled to 0°C. Then, DIPEA (17.2 ml) and the acid chloride were successively added, and the mixture was stirred at 0° C.
  • 6-(trifluoromethyl)-4-((trifluoromethyl)thio)pyridin-3-amine (0.11 g) was dissolved in THF (2.1 ml) and cooled to 0° C. Then, TEA (0.18 ml), triphosgene (0.12 g), and a catalytic amount of DMAP were added, and the mixture was stirred at room temperature for 1 hour.
  • reaction liquid was then evaporated under reduced pressure, and the residue was suspended in THF (2.1 ml), 1-(3-cyclopropyl-1-(pyrimidin-2-yl)-1H-1,2,4-triazol-5-yl)ethan-1-amine (0.13 g) and TEA (0.12 ml) were added, and the mixture was stirred at room temperature for 5 hours.
  • Water was then added to the reaction solution, which was then extracted with ethyl acetate and washed with saturated saline, and the organic layer was dried over anhydrous magnesium sulfate.
  • the solvent was then distilled off under reduced pressure, and the resulting concentrate was purified by silica gel column chromatography to obtain the target compound (0.15 g).
  • 6-(trifluoromethyl)pyridin-3-amine (10.0 g) was dissolved in dichloromethane (150 ml), TEA (10.3 ml) and DMAP (0.75 g) were added, and the mixture was cooled to 0° C. Then, BocO (14.9 ml) was added, and the mixture was stirred at room temperature overnight. Water was then added to the reaction solution, which was then extracted with ethyl acetate and washed with saturated saline, and the organic layer was dried over anhydrous magnesium sulfate. The solvent was then distilled off under reduced pressure, and the resulting concentrate was purified by silica gel column chromatography to obtain the target compound (9.4 g). Yield: 58%.
  • tert-butyl (6-(trifluoromethyl)pyridin-3-yl)carbamate (10.86 g) was dissolved in THF (140 ml), TMEDA (15.4 ml) was added, and the mixture was cooled to ⁇ 78° C. Then, a 2.64 M nBuLi hexane solution (39 ml) was added dropwise, and the mixture was further stirred at ⁇ 78° C. for 1 hour. Then, 1,2-dibromoethane (8.8 ml) was added, the temperature was raised to room temperature, and the mixture was further stirred for 5 hours.
  • tert-butyl (4-bromo-6-(trifluoromethyl)pyridin-3-yl)carbamate (8.18 g) was dissolved in 120 ml of toluene, and trifluoroethanol (12.0 g), cesium carbonate (15.6 g), tBuXPhos (0.61 g), and Pd2(dba)3 (0.66 g) were added in that order, and the mixture was stirred at 80°C for 6 hours. Water was then added to the reaction mixture, which was then extracted with ethyl acetate and washed with saturated saline, and the organic layer was dried over anhydrous magnesium sulfate.
  • tert-butyl (1-(1-(6-chloropyrimidin-4-yl)-1H-1,2,4-triazol-5-yl)ethyl)carbamate (0.65 g) was dissolved in DMF (8.0 ml), and zinc cyanide (0.71 g) and Pd( PPh3 ) 4 (0.23 g) were added successively and stirred at 80°C for 6 hours under a nitrogen atmosphere. Water was then added to the reaction solution, which was then extracted with ethyl acetate and washed with saturated saline, and the organic layer was dried over anhydrous magnesium sulfate.
  • Step 2 Synthesis of 1-(1-(1-(6-cyanopyrimidin-4-yl)-1H-1,2,4-triazol-5-yl)ethyl)-3-(4-(2,2,2-trifluoroethoxy)-6-(trifluoromethyl)pyridin-3-yl)urea
  • tert-butyl (1-(1-(6-cyanopyrimidin-4-yl)-1H-1,2,4-triazol-5-yl)ethyl)carbamate (0.41 g) was dissolved in dichloromethane (10 ml) and cooled to 0° C. Then, trifluoroacetic acid (1.5 g) was added and the mixture was stirred at room temperature for 4 hours. The reaction mixture was then evaporated under reduced pressure to give 6-(5-(1-aminoethyl)-1H-1,2,4-triazol-1-yl)pyrimidine-4-carbonitrile.
  • tert-butyl (1-(1-(5-(difluoromethoxy)pyrimidin-2-yl)-1H-1,2,4-triazol-5-yl)ethyl) carbamate (0.64 g) was dissolved in dichloromethane (12 ml), and 4M hydrochloric acid in 1,4-dioxane (2.2 ml) was added thereto, followed by stirring at room temperature overnight. The reaction mixture was then evaporated under reduced pressure to give crystals which were then used in the next step.
  • LCMS retention times were determined in the following manner.
  • a Waters CORTECS UPLC C18 column (Waters, 2.1 x 50 mm, 1.6 ⁇ m) was attached to a system consisting of an ultra-high performance, high-resolution liquid chromatograph (ACQUITY UPLC H-Class: manufactured by Waters), an ACQUITY UPLC photodiode array (PDA) e ⁇ detector (manufactured by Waters), and an ACQUITY QDa detector (positive and negative ion electrospray mode, UV PDA detection, manufactured by Waters), and measurements were performed at a temperature of 40°C, a flow rate of 0.6 mL/min, and 2 ⁇ L injection.
  • ACQUITY UPLC H-Class manufactured by Waters
  • PDA photodiode array
  • QDa detector positive and negative ion electrospray mode, UV PDA detection, manufactured by Waters
  • the concentration of the mobile phase (B) was maintained at 30% by mass for 0.15 minutes, then the concentration of the mobile phase (B) was increased from 30% by mass to 95% by mass at a constant rate over 1.35 minutes, maintained at 95% by mass for 0.5 minutes, then the concentration of the mobile phase (B) was immediately decreased to 30% by mass, and finally the concentration of the mobile phase (B) was maintained at 30% by mass for 0.50 minutes.
  • Table 1 shows a group of compounds prepared by the same method, including the compounds listed in the synthesis examples. Table 1 also lists the melting points as physical properties of the compounds.
  • Test Example 1 Efficacy test against armyworm Emulsion (I) was diluted with water to a set concentration to obtain a dilution (I). Emulsion (II) was diluted with water to a set concentration to obtain a dilution (II). Corn leaf pieces were immersed in dilution (I) and dilution (II) for 30 seconds. The immersion-treated corn leaf pieces were placed in a petri dish, and five second-instar armyworm larvae were released into the dish. The petri dish was left in a thermostatic chamber at a temperature of 25°C and a humidity of 60%. Six days after the release of the insects, the survival rate was determined and the mortality rate was calculated. The test was carried out in duplicate. The results of the test are shown in Table 2 below, which shows the insecticidal rate of each compound at the concentration shown in the table.
  • Emulsion (I) was diluted with water to a set concentration to obtain a dilution (I).
  • Emulsion (II) was diluted with water to a set concentration to obtain a dilution (II).
  • Cabbage leaves were immersed in each of dilution (I) and dilution (II) for 30 seconds. After the immersion treatment, the cabbage leaves were air-dried and placed in a petri dish, into which five second-instar larvae of Spodoptera litura were released. The petri dish was left in a thermostatic chamber at a temperature of 25°C and a humidity of 60%. Six days after the release of the insects, the survival rate was determined and the mortality rate was calculated. The test was carried out in duplicate. The results of the test are shown in Table 3 below, which shows the insecticidal rate of each compound at the concentration shown in the table.
  • Emulsion (I) was diluted with water to a set concentration to obtain dilution (I).
  • Emulsion (II) was diluted with water to a set concentration to obtain dilution (II).
  • Dilution (I) and dilution (II) were sprayed on bok choy seedlings (at the seventh true leaf development stage) planted in 3-inch pots.
  • the bok choy seedlings were air-dried and then placed in plastic cups.
  • Ten adult Striata stripes flea beetles were released into the cups and stored in a thermostatic chamber at a temperature of 25°C and a humidity of 65%. Seven days after the release of the insects, the survival rate was determined and the mortality rate was calculated.
  • the test was carried out in duplicate. The results of the test are shown in Table 9 below, which shows the insecticidal rate of each compound at the concentration shown in the table.
  • Emulsion (I) was diluted with water to a set concentration to obtain dilution (I).
  • Emulsion (II) was diluted with water to a set concentration to obtain dilution (II).
  • Dilution (I) and dilution (II) were sprayed onto green bean leaf disks and air-dried. Seven days after spraying, the survival rate was determined and the mortality rate was calculated. The test was carried out in duplicate. The results of the test are shown in Table 11 below, which shows the insecticidal rate of each compound at the concentration shown in the table.
  • Control rate (%) ⁇ (Mc)-(Mt)/(Mc) ⁇ x 100
  • Mc Number of mines with a total length of 1 cm or more in the untreated area
  • Mt Number of mines with a total length of 1 cm or more in the spray-treated area
  • the (hetero)aryl urea compound of the present invention has excellent insecticidal activity, is safe, and can be synthesized industrially advantageously.
  • the insecticide of the present invention can effectively control agricultural pests at low concentrations.

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  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne un composé représenté par la formule (I) ou un sel de celui-ci. Dans la formule (I) : A1 est un atome d'azote ou un groupe représenté par CH ; R1 représente un groupe haloalcoxy en C1-6 ou un groupe haloalkylthio en C1-6 ; Ra est un atome d'hydrogène ou un groupe cycloalkyle en C3-6 substitué ou non substitué ; B1 est un atome d'azote ou un groupe représenté par CH ; B2 est un atome d'azote ou un groupe représenté par CXb ; et Xa et Xb sont indépendamment un atome d'hydrogène, un groupe haloalcoxy en C1-6, un groupe halogéno, un groupe carbamoyle, un groupe thiocarbamoyle ou un groupe cyano.
PCT/JP2023/038749 2022-11-10 2023-10-26 Composé d'urée (hétéro)aryle et insecticide WO2024101172A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62185065A (ja) * 1986-01-30 1987-08-13 チバ−ガイギ−　アクチエンゲゼルシヤフト Ｎ−〔４−（ハロアルコキシ）トリフルオロメチルフエニル〕−ｎ′−ベンゾイル尿素、その製造方法及び有害生物を防除するためのその使用方法
JP2017523162A (ja) * 2014-07-23 2017-08-17 ダウ アグロサイエンシィズ エルエルシー ある種の農薬的利用性を有する分子、それに関する中間体、組成物および方法
WO2020229398A1 (fr) * 2019-05-14 2020-11-19 Bayer Aktiengesellschaft Triazoles et pyrazoles à substitution (1-alcényl) utilisés comme pesticides
WO2022157188A2 (fr) * 2021-01-23 2022-07-28 Syngenta Crop Protection Ag Composés hétéroaromatiques à action pesticide
WO2022244795A1 (fr) * 2021-05-21 2022-11-24 日本曹達株式会社 Composé hétéroaryle et agent de lutte contre les nuisibles

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62185065A (ja) * 1986-01-30 1987-08-13 チバ−ガイギ−　アクチエンゲゼルシヤフト Ｎ−〔４−（ハロアルコキシ）トリフルオロメチルフエニル〕−ｎ′−ベンゾイル尿素、その製造方法及び有害生物を防除するためのその使用方法
JP2017523162A (ja) * 2014-07-23 2017-08-17 ダウ アグロサイエンシィズ エルエルシー ある種の農薬的利用性を有する分子、それに関する中間体、組成物および方法
WO2020229398A1 (fr) * 2019-05-14 2020-11-19 Bayer Aktiengesellschaft Triazoles et pyrazoles à substitution (1-alcényl) utilisés comme pesticides
WO2022157188A2 (fr) * 2021-01-23 2022-07-28 Syngenta Crop Protection Ag Composés hétéroaromatiques à action pesticide
WO2022244795A1 (fr) * 2021-05-21 2022-11-24 日本曹達株式会社 Composé hétéroaryle et agent de lutte contre les nuisibles

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