Substituted pyridyl phenyl oxazoline derivative and method for controlling pests using same

Abstract

[Problem] To provide a new compound having a sufficient effect on pests which have developed resistance and are difficult to control and on which a known compound does not exhibit any effects. [Solution] A substituted pyridyl phenyl oxazoline derivative compound represented by formula (1). [In the formula, R1 represents a C1-C6 perfluoroalkyl group or a C1-C6 perfluoroalkylthio group, and R2 represents a halogen atom].

Description

Substituted pyridylphenyloxazoline derivatives and methods for controlling pests associated with them

[0001] This invention relates to substituted pyridylphenyloxazoline derivatives and the use of these compounds as pest control agents.

[0002] Pesticides are useful materials for protecting crops from diseases and pests, and for reducing labor in farming and improving agricultural productivity. Among these pesticides, compounds with an oxazoline ring structure have been studied and put into practical use for the purpose of controlling harmful organisms. For example, the disclosures in Patent Documents 1 to 5 are relevant. On the other hand, reports on the development of insecticide resistance in harmful organisms are continuously increasing. For example, thrips are known as difficult-to-control pests, and many populations that have developed further resistance to pesticides have been reported. Therefore, in agriculture, there is a constant need for the development of pesticides that are highly effective against resistant pests that existing pesticides are ineffective against. Although several oxazoline derivative compounds have been disclosed with the aim of being effective against resistant pests, their effectiveness against current resistant pests is not sufficient. In agriculture, there is a constant need for novel compounds that are highly effective against pests resistant to existing pesticides.

[0003] Japanese Patent Publication No. 2000-503013, Japanese Patent Publication No. 2002-518389, Japanese Patent Publication No. 10-512859, Japanese Patent Publication No. 2004-536828, U.S. Patent US 6573286

[0004] The problem that this invention aims to solve is to provide a novel compound that has sufficient effect against difficult-to-control pests that have developed resistance, to which known compounds are ineffective.

[0005] As a result of diligent research to solve the aforementioned problems, the inventors have discovered that a pyridylphenyloxazoline derivative having a specific structure exhibits remarkable insecticidal and acaricidal effects against individuals of various pests that have developed high resistance to multiple types of pesticides. Based on this finding, the present invention has been completed. The main aspects of the present invention are as follows: [1] Formula (1): [In the formula, R １ R represents a C1-C6 perfluoroalkyl group or a C1-C6 perfluoroalkylthio group. ２ represents a halogen atom. ] A substituted pyridylphenyloxazoline derivative compound represented by ]. [2] R ２ The compound described in [1], wherein is a fluorine atom or a chlorine atom. [3] R １ The compound described in [1], wherein is a C1-C4 perfluoroalkyl group or a C3-C4 perfluoroalkylthio group. [4] R １ The compound described in [3], wherein is a C3-C4 perfluoroalkyl group or a C3-C4 perfluoroalkylthio group. [5] R １ The compound described in [1], wherein is a C1-C6 perfluoroalkyl group. [6] R １ The compound according to [5], wherein the compound is a C3-C4 perfluoroalkyl group. [7] A pest control agent containing the compound according to any one of [1] to [6] and an auxiliary agent. [8] A method for controlling pests, comprising applying an effective amount of the compound according to any one of [1] to [6]. [9] The method according to [8], comprising applying an effective amount of the compound according to any one of [1] to [6] to a pest or a plant inhabited by a pest or to the soil in which the plant is cultivated.

[0006] The compounds of the present invention have excellent control activity against harmful organisms. These compounds also exhibit excellent control activity against highly resistant and difficult-to-control harmful organisms that cannot be controlled by known compounds.

[0007] In this specification, expressions such as "Ca to Cb" preceding each substituent mean that the corresponding group contains a to b carbon atoms. "Halogen atoms" include fluorine, chlorine, bromine, and iodine atoms. "Alkyl" as used in the group itself or in part of the group can be linear or branched, and is not limited to these, but examples include methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-pentyl, and n-hexyl, each selected within the specified range of carbon atoms. "Perfluoroalkyl" means that the alkyl portion has the above meaning, and all hydrogen atoms bonded to carbon atoms are replaced by fluorine atoms. It is not limited to these, but examples include trifluoromethyl, pentafluoroethyl, heptafluoro-n-propyl, heptafluoro-iso-propyl, nonafluoro-n-butyl, nonafluoro-iso-butyl, nonafluoro-sec-butyl, nonafluoro-tert-butyl, undecafluoro-n-pentyl, and tridecafluoro-n-hexyl, each selected within the specified range of carbon atoms. "Perfluoroalkylthio" means a perfluoroalkyl-S- group having the above-described meaning in the perfluoroalkyl portion, and is not limited to this, but examples include trifluoromethylthio, pentafluoroethylthio, heptafluoro-n-propylthio, heptafluoro-iso-propylthio, nonafluoro-n-butylthio, nonafluoro-iso-butylthio, nonafluoro-sec-butylthio, nonafluoro-tert-butylthio, undecafluoro-n-pentylthio, and tridecafluoro-n-hexylthio, and each is selected within the specified range of carbon atoms.

[0008] The compounds of formula (I) included in the present invention have optically active forms due to the presence of one or more chiral carbon atoms, but the present invention includes all optically active forms or racemic mixtures.

[0009] In a compound of formula (I) encompassed by the present invention, R １Examples of the substituent represented by include a C1-C6 perfluoroalkyl group or a C1-C6 perfluoroalkylthio group. Among these, a C1-C4 perfluoroalkyl group or a C3-C4 perfluoroalkylthio group is preferable, a C3-C4 perfluoroalkyl group or a C3-C4 perfluoroalkylthio group is more preferable, and a C3-C4 perfluoroalkyl group is particularly preferable. In the compound of formula (I) included in the present invention, R ２ Examples of the substituent represented by include a halogen atom. Among these, a fluorine atom or a chlorine atom is preferable. As the compound of formula (I) included in the present invention, R １ Examples of the compound in which the substituent represented by is a C1-C6 perfluoroalkyl group or a C1-C6 perfluoroalkylthio group and the substituent represented by R ２ is a halogen atom include those in which the substituent represented by R １ is a C1-C4 perfluoroalkyl group or a C3-C4 perfluoroalkylthio group and the substituent represented by R ２ is a fluorine atom or a chlorine atom are preferable, those in which the substituent represented by R １ is a C3-C4 perfluoroalkyl group or a C3-C4 perfluoroalkylthio group and the substituent represented by R ２ is a fluorine atom or a chlorine atom are more preferable, and those in which the substituent represented by R １ is a C3-C4 perfluoroalkyl group and the substituent represented by R ２ is a fluorine atom or a chlorine atom are particularly preferable.

[0010] Next, the method for producing the compound of the present invention will be described.

[0011] The compound of the present invention can be produced, for example, by the following production methods.

[0012] In all the formulas listed below, the substituents and symbols have the same meanings as defined for formula (1) unless otherwise defined.

[0013] <Method for producing pyridylphenyloxazoline derivative (1)> The compound of formula (1) provided by the present invention can be produced by the following method.

[0014] A method for producing the compound of formula (1) is characterized by reacting an amino alcohol derivative represented by formula (2) with 2,6-difluorobenzoyl chloride represented by formula (3) in the presence of a base to obtain the amide alcohol compound of formula (4), which is then reacted with methanesulfonyl chloride to obtain formula (5), and then cyclized in the presence of a base to obtain the oxazoline derivative of formula (6). The obtained compound of formula (6) is then subjected to a Suzuki-Miyaura coupling reaction with a substituted pyridylboronic acid (7) or its pinacol ester (8). This reaction can be carried out by referring to known reaction conditions (for example, see Japanese Patent Publication No. 11-513663, WO9741091, Chem. Rev. 1995, 95, 2457-2483, Eur. J. Med. Chem. 2017, 140, 528-541). (In the formula, Y represents a bromine atom or an iodine atom.)

[0015] <Method for producing amino alcohol derivative (2)> The amino alcohol derivative of formula (2), which is used as a starting material in the production of the compound of formula (1), can be produced by any of the following methods (A1), (A2), or (A3).

[0016] Method (A1): A method for producing the compound of formula (2), characterized by alkylating the substituted phenylacetic acid shown in formula (9) to obtain the ester of formula (10), then reacting it with a nitrite ester in the presence of a base to synthesize the oxime ester derivative of formula (11), and then carrying out a reduction reaction. This reaction can be carried out by referring to known reaction conditions (see, for example, Japanese Patent Publication No. 11-513663 and Japanese Patent Publication No. 2008-524333). (In the formula, R ３ (This represents a methyl group or an ethyl group.)

[0017] Method (A2): A method for producing the compound of formula (2), characterized by reacting a commercially available substituted benzene represented by formula (12) with a chloroglyoxylate ester in the presence of a Lewis acid to obtain the ketoester of formula (13), and then reacting the resulting compound of formula (11) with hydroxylamine hydrochloride in the same manner as in method (A1). This reaction can be carried out by referring to known reaction conditions (for example, see Japanese Patent Publication No. 11-513663).

[0018] Method (A3): A method for producing the compound of formula (2), characterized by first converting a commercially available substituted benzaldehyde represented by formula (14) into an epoxide of formula (15), then reacting it with sodium azide to produce an azide alcohol of formula (16), and then carrying out a Staudinger reaction. This reaction can be carried out by referring to known reaction conditions (see, for example, Tetrahedron, 2009, 65(39), 8199-8205, J. Org. Chem. 2008, 73(6), 2270-2274).

[0019] <Method for producing pyridylboronic acid (7) and pyridylboronic acid pinacol ester (8)> The compounds of formula (7) and formula (8) used in the production of the compound of formula (1) are commercially available or can be produced by either method (B1) or (B2).

[0020] Method (B1): A method for producing a compound of formula (7) or formula (8), characterized by reacting 3-aminopyridine with a perfluoroalkyl iodide to obtain formula (17), and then producing the compound of formula (17) via a substituted halogenopyridine (18) or directly from the substituted aminopyridine (17). This reaction can be carried out by referring to known reaction conditions (see, for example, EP1006102, Angew. Chem., Int. Ed. 2010, 49(10), 1846-1849, J. Org. Chem. 1995, 60, 7508-7510, Org. Lett. 2011, 13(17), 4479-4481). (In the formula, R １ (This represents a C1-C6 perfluoroalkyl group.)

[0021] Method (B2): A method for producing a compound of formula (7) or formula (8), characterized by converting a commercially available substituted pyridinone represented by formula (19) to the pyridinethion compound of formula (20) using Lawson's reagent, reacting it with a perfluoroalkyl iodide in the presence of a base to obtain formula (18), and then carrying out the same reaction as in method (B1). This reaction can be carried out by referring to known reaction conditions (see, for example, US20120309796 and WO2015086506). (In the formula, R １ (This represents a C1-C6 perfluoroalkylthio group.)

[0022] Examples of harmful organisms that the compounds and pest control agents of the present invention are effective against include harmful insects and harmful mites. Specifically, examples of such harmful organisms include the following:

[0023] Pests of the order Hemiptera: Planthoppers such as Laodelphax striatellus, Nilaparvata lugens, Sogatella furcifera, and Peregrinus maidis; leafhoppers such as Nephotettix cincticeps, Nephotettix virescens, Rice green leafhopper (Nephotettix nigropictus), Recilia dorsalis, and Empoasca Leafhoppers such as onukii, potato leaf hopper (Empoasca fabae), corn leaf hopper (Dalbulus maidis), sugarcane froghopper (Mahanarva posticata), sugarcane root spittles (Mahanarva fimbriota), white leafhopper (Cofana spectra), black-striped leafhopper (Nephotettix nigropictus), cotton aphid (Aphis gossypii), peach aphid (Myzus persicae), and radish aphid (Brevicoryne) Brassicae, Spiraea aphid (Aphis spiraecola), Tulip aphid (Macrosiphum euphorbiae), Potato aphid (Aulacorthum solani), Wheat aphid (Rhopalosiphum padi), Citrus aphid (Toxoptera citricidus), Peach aphid (Hyalopterus pruni), Soybean aphid (Aphis gycynes matsumura), Corn aphid (Rhopalosiphum maidis), Rhopalosiphum tetraneura nigriabdominalis), grape aphid (Viteus v. jpgoliae), Grape Phylloxera (Daktulosphaira v. jpgoliae),Aphids such as Pecan phylloxera (Phylloxera devastatrix Pergande), Pecan leaf phylloxera (Phylloxera notabilis Pergande), Southern pecan leaf phylloxera (Phylloxera russellae Stoetzel), rice black bug (Scotinophara lurida), Malayan rice black bug (Scotinophara coarctata), and green stink bug (Nezara) antennata), Eysarcoris parvus, Halyomorpha mista, Nezara viridula, Brown stink bug (Euschistus heroes), Southern green stink bug (Nezara viridula), Red banded stink bug (Piezodorus guildinii), Burrower brown bug (Scaptocoris castanea), Oebalus pugnax, Dichelops Stink bugs such as Melacanthus, Reptortus clavetus, Leptocorisa chinensis, Leptocorisa acuta, Leptocorisa species, Trigonotylus caelestialium, Stenotus rubrovittatus, Lygus lineararius, and Chinchi bug (Blissus leucopterus) Miridae such as Leucopterus, greenhouse whiteflies (Trialeurodes vaporariorum), tobacco whiteflies (Bemisia tabaci), citrus whiteflies (Dialeurodes citri), citrus spiny whiteflies (Aleurocanthus spiniferus), and other whiteflies.Red scale insect (Aonidilla aurantii), San Jose scale insect (Comstoccaspis perniciosa), Citrus snow scale insect (Unaspis citri), Ruby scale insect (Ceroplastes rubens), Icerya scale insect (Icerya purchasi), Fuji scale insect (Planococcus kraunhiae), Mulberry scale insect (Pseudaucoccus longispinis), Mulberry white scale insect (Pseudaulacaspis pentagona), Tuttlemee bug (Brevennia) Scale insects such as *rehi*, psyllids such as *Diaphorina citri*, *Psylla pyrisuga*, and *Bactericerca cockerelli*, lace bugs such as *Stephanitis nasi*, bed bugs such as *Cimex lectularius*, and giant cicada (Quesada gigas).

[0024] Lepidopteran pests: Chilo suppressalis, Darkheaded stem bore (Chillo polychrysus), Triporyza incertulas, Tropical stem borer (Chillo polychrysus), White stem borer (Scirpophaga innotata), Yellow stem bore (Scirpophaga incertulas), Pink bore (Sesamia inferens), Rupela albinella, Rumex rotundifolius (Cnaphalocrocis medinalis), Marasmia Patnalis, Marasmia exigna, Cotton borer (Notarcha derogata), Indian meal moth (Plodia interpunctella), Corn borer (Ostrinia furnacalis), Diamondback moth (Hellula undalis), Sod web moth (Pediasia teterrellus), Rice case worm (Nymphula depunctalis), Marasmia genus, Hop vine bore (Hydraecia immanis), European corn bore (Ostrinia nubilalis), Lesser cornstalk Moths such as bore (Elasmopalpus lignosellus), Bean Shoot Borer (Epinotia aporema), Sugarcane Borer (Diatraea saccharalis), Giant Sugarcane Borer (Telchin licus), beet armyworm (Spodoptera litura), white-striped armyworm (Spodoptera exigua), foxtail armyworm (Pseudaletia separata), cutworm (Mamestrata brassicae), and rice armyworm (Sesamia) inferens), Spodoptera mauritia, Spodoptera frugiperda, Spodoptera exceptta, Agrotis ipsilon,Plusia nigrisigna, Soybean looper (Pseudoplusia includens), Trichoprusia, Heliothys virescences and other Heliothys species, Helicoverpa armigera and other Helicoverpa species, Velvetbean caterpillar (Anticarsia gammatalis), Cotton leafworm (Alabama argillacea) and other noctuid moths, Pieris rapae and other white butterflies, Adoxophies species, Pear leaf moth (Grapholita) Tortricidal moths such as molesta, bean pod moth (Leguminivora gycinivorella), adzuki bean pod moth (Matsumuraeses azukivora), apple tortrix moth (Adoxophyes orana fasciata), tea tortrix moth (Adoxophyes honmai.), tea tortrix moth (Homona magnanima), variegated tortrix moth (Archips fuscocupreanus), codling moth (Cydia pomonella), tea leaf roller moth (Caloptilia theivora), golden leaf roller moth (Phyllonorecter) Narrow-legged moths such as ringoneella, fruit moths such as Carposina niponensis and Citrus fruit bore (Ecdytolopha aurantiana), leaf miners such as coffee leaf miner (Leucoptera coffeela) and Lyonetia, poisonous moths such as Limantria and Euplocthys, diamondback moths such as Plutella xylostella, cotton beetles such as Pectinophora gossypierla and potato moth (Phyromaea operculella), and fall webworms (Hyphantria) Tribatid species such as *Cunea*.

[0025] Thrips pests: Thrips species such as the citrus yellow thrips (Frankliniella occidentalis), southern yellow thrips (Thrips parmi), tea yellow thrips (Scirtothrips dorsalis), onion thrips (Thrips tabaci), flat-headed flower thrips (Frankliniella intonsa), Western flower thrips (Frankliniella occidentalis), rice thrips (Haplothrips aculeatus), and rice thrips (Stenchaetothrips biformis).Diptera pests: Culex pipiens pallens, Culex tritaeniorhynchus, Culex quinquefasciatus and other house mosquitoes; Aedes species such as Aedes aegypti and Aedes albopictus; Anopheles species such as Anopheles sinensis; midges; houseflies such as Musca domestica and Muscina stabulans; seed flies (Delia platura), onion flies (Delia Flower flies such as *Antiqua*, sugar beetroot maggot (Tetanops myopaeformis), leafminers such as rice leafminer (Agromyza oryzae), rice leafminer (Hydrellia griseola), tomato leafminer (Liriomyza sativae), bean leafminer (Liriomyza trifolii), and leafminer (Chromatomyia horticola), leafminers such as rice leafminer (Chlorops oryzae), melon flies (Dacus cucurbitae), Mediterranean fruit flies (Ceratitis) Fruit flies such as *Capitata*, shore flies such as *Hydrellia philippina* and *Hydrellia sasakii*, fruit flies, phorid flies such as *Megaselia spiracularis*, drain flies such as *Clogmia albipunctata*, fungus gnats, gall midges such as *Mayetiola destroyer* and *Orseolia oryzae*, hammerhead flies such as *Diopsis macrophthalma*, Common Crane flies such as the common crane fly (Tipula oleracea) and the European crane fly (Tipula paludosa).

[0026] Coleopteran pests: Western corn rootworm (Diabrotica virgifera virgifera), Southern corn rootworm (Diabrotica undecimpunctata howardi), Northern corn rootworm (Diabrotica barberi), Mexican corn rootworm (Diabrotica virgifera zeae), Banded cucumber beetle (Diabrotica balteata LeConte), San Antonio beetle (Diabrotica speciosa), Cucurbit beetle (Diabrotica speciosa), Bean leaf beetle (Cerotoma) trifurcata, cereal leaf beetle (Oulema melanopus), cucumber beetle (Aulacophora femoralis), striped flea beetle (Phyllotreta striolata), Colorado leaf beetle (Leptinotarsa ​​decemlineata), rice leaf beetle (Oulema oryzae), grape colaspis (Colaspis brunnea), corn flare beetle (Chaetocnema pulicalia), potato flare beetle (Epitrix cucumeris), rice spine beetle (Dicladispa armigera), seedcorn beetle (Stenolophus) Leaf beetles such as *lecontei*, Slender seedcorn beetle (Clivinia impressifrons), Japanese beetle (Anomala cuprea), Japanese dung beetle (Anomala rufocuprea), Japanese beetle (Popillia japonica), European chafer (Rhizotrogus majalis), carrot beetle (Bothynus gibbosus), Grape Colaspis (Colaspis brunnea), southern corn leaf beetle (Myochrous) Scarab beetles such as *Denticollis*, *Holotricia*, and *Phyllophaga* species including the June beetle (*Phyllophaga crinita*),Rice weevils such as Sitophilus zeamais, Echinocnemus squameus, Lissorhoptrus oryzophilus, and Sphenophorus venatus, as well as cotton weevils (Anthonomus grandis), Southern Corn Billbug (Sphenophorus callosus), Soybean stick weevil (Sternechus subsignatus), and Sphenophorus Weevils such as Levis and other species of the genus Sphenophorus, Epilachna species such as the 28-spotted ladybug (Epilachna vigintioctopunctata), bark beetles such as Lyctus brunneus and Tomicus piniperda, longhorn beetles, leaf beetles, longhorn beetles such as Anoplophora malasiaca and Migdolus fryanus, Okinawa click beetles (Melanotus okinawensis) and brown-brown click beetles (Agriotes ogurae) Click beetles such as *Fuscicollis*, *Melanotus legatus*, *Agriotes sp.*, *Aelous sp.*, *Anchastus sp.*, *Melanotus sp.*, *Limonius sp.*, *Conoderus sp.*, *Ctenicera sp.*, *Paederus fuscipes*, and other rove beetles, as well as the Coffee Barry Borer (Hypothenemus hampei).

[0027] Grasshopper pests: Migratory locust (Locusta migratoria), mole cricket (Gryllotalpa africana), Moroccan grasshopper (Dociostaurus maroccanus), Australian grasshopper (Chortoicetes terminifera), Red grasshopper (Nomadacris septemfasciata), Brown grasshopper (Locusta na pardalina), Tree grasshopper (Anacridium melanorhodon), Italian grasshopper (Calliptamus italicus), Differential grasshopper (Melanoplus differentialis), Twostripped grasshopper (Melanoplus bivittatus), Migratory grasshopper (Melanoplus sanguinipes), Red-Legged grasshopper (Melanoplus femurrubrum), Clearwinged grasshopper (Camnula Yellow-winged locust (Gastrimargus), Yellow-winged locust (Schistocerca gregaria), Crickets such as *musicus*, *Spur-throated locust* (Austracris guttulosa), *Oxya yezoensis*, *Oxya japonica*, *Patanga succincta*, *Acheta domesticus*, and *Teleogryllus emma*, *Anabrus simplex*, and other types of crickets. Hymenoptera pests: Sawflies such as the cabbage sawfly (Athalia rosae) and the Japanese cabbage wasp (Athalia japonica), fire ants, and leafcutter ants such as the brown leaf-cutting ant (Atta capiguara).

[0028] Cockroach pests: German cockroach (Blattella germanica), Oriental cockroach (Periplaneta fuliginosa), American cockroach (Periplaneta amelicana), Brown cockroach (Periplaneta brunnea), Eastern cockroach (Blatta orientalis). Termite pests: Japanese subterranean termite (Reticulitemes speratus), Formosanus subterranean termite (Coptotermes formosanaus), Incisitermes minor, Cryptotermes domesticus, Odontotermes formosanaus, Neotermes koshunensis, Glyptotermes satsumensis, Glyptotermes nakajimai, and Coptotermes species. fuscus), Kodama termite (Glyptotermes kodamai), Kushimoto termite (Glyptotermes kushimensis), Large termite (Hodotermopsis sjostedti), Koshu termite (Coptotermes guangzhoensis), Amami termite (Reticulitermes amamianus), Miyatake termite (Reticulitermes miyatakei), Kanmon termite (Reticulitermes kanmonensis.), Takasago termite (Nasutitermes takasagoensis), Nitobe termite (Pericapritermes) Examples include *Cornite nitobei*, *Sinocapritermes mushae*, and *Cornitermes cumulans*.

[0029] Acari pests: Spider mites such as Tetranychus urticae, Tetranychus kanzawai, Panonychus citri, Panonychus ulmi, Oligonicus species and Southern Turkey spider mites (Brevipalpus phoenicis), Aculops pelekassi, Phyllocoptruta citri, Aculops lycopersici, and Calacarus Gall mites such as *Carinatus*, *Acapylella theavagrans*, *Eriophyes chibaensis*, and *Aculus schlechtendali*; dust mites such as *Polyphagotarsonemus latus*; small spider mites such as *Brevipalpus phoenicis*; long-haired spider mites; *Haemaphysalis longicornis*, *Haemaphysalis flava*, and *Dermacenter*. Ticks such as *Ixodes taiwanicus*, *Dermacenter variabilis*, *Ixodes ovatus*, *Ixodes persulcatus*, *Ixodes scapularis*, *Amblyoma americanum*, *Boophilus microplus*, *Rhipicephalus sanguineus*, *Tyrophagus putrescentiae*, and *Tyrophagus* Dust mites such as *Dermatophthosis similis*, house dust mites such as *Dermatophthosis farinae* and *Dermatophthosis ptrenyssnus*,Cheyletus eruditus, Cheyletus malaccensis, Cheyletus morei, Cheyletiella yasguri, and other Cheyletiella mites; Octodectes cynotis, Sarcoptes scabiei, and other Sarcoptes scabiei mites; Demodex canis and other Demodex mites; Head mites; Oribatid mites; House mites (Ornithonyssus bacoti), and Bird mites (Ornithonyssus) Mice such as *Sylvairum*, *Dermanyssus gallinae*, and other types of mite mite species, and scrub mites such as *Leptotrombidium akamushi*. Spiders: *Chiracanthium japonicum*, *Latrodectus hasseltii*, etc. Chilopoda: *Thereuonema hilgendorfi*, *Scolopendra subsp. nipes*, etc. Diplopoda: Millipedes (Oxidus gracilis), Millipedes (Nedyopus tambanus), etc. Isopoda: Pill bugs (Armadillidium vulgare), etc. Gastropoda: Brown slugs (Limax marginatus), Yellow slugs (Limax flavus), Apple snails (Pomacea canaliculata), etc.

[0030] Examples of harmful nematodes include the following:

[0031] Harmful nematodes: Aphelenchoides spp. such as Aphelenchoides besseyi, Pratylenchus spp. such as Pratylenchus coffeae, Pratylenchus brachyurus, Pratylenchus neglectus, Meloidogyne spp. such as Meloidogyne javanica, Meloidogyne incognita, Meloidogyne hapla, Heterodera spp. such as Heterodera glycines, Globodera spp. such as Globodera rostochiensis, Rotylenchulus reniformis, Nothotylenchus acris, Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaphelenchus spp. such as Bursaphelenchus xylophilus, etc.

[0032] The compound of formula (1) of the present invention can be used alone, but usually, according to a conventional method, an auxiliary agent or the like is blended with the compound of formula (1). Although not limited, for example, powders, emulsions, oils, solubilizers, suspoemulsion agents, fine particles, aerosol agents, DL powders, fine particles F, fine granules F, granules, wettable powders, granular wettable powders, flowables, tablets, pastes, oily suspensions, water-soluble agents, granular water-soluble agents, liquids, microcapsules, etc. It is preferably formulated into any dosage form and used. The pest control agent of the present invention usually contains the compound of the present invention in an amount of 0.01 to 95% by weight.

[0033] Examples of the auxiliary agents that can be used in the formulation include, but are not limited to, solid carriers, liquid carriers, binders, thickeners, surfactants, antifreezing agents, preservatives, antifoaming agents, and the like.

[0034] Examples of the solid carriers used in the formulation include, but are not limited to, talc, bentonite, montmorillonite, clay, kaolin, calcium carbonate, sodium carbonate, sodium bicarbonate, mirabilite, zeolite, starch, acid clay, diatomaceous earth, white carbon, vermiculite, slaked lime, vegetable powders, alumina, activated carbon, saccharides, glass hollow bodies, silica sand, ammonium sulfate, urea, and the like.

[0035] Examples of the liquid carriers used in the formulation include, but are not limited to, hydrocarbons (kerosene, mineral oil, etc.), aromatic hydrocarbons (toluene, xylene, dimethylnaphthalene, phenylxylylethane, etc.), halogenated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), acid amides (DMF, dimethylacetamide, etc.), sulfoxides (DMSO, etc.), propylene carbonate, vegetable oils (soybean oil, cottonseed oil, etc.), water, and the like.

[0036] The surfactants are not limited to these, but examples include fatty acid salts, benzoates, alkyl sulfosuccinates, dialkyl sulfosuccinates, polycarboxylates, alkyl sulfates, alkyl sulfates, alkylaryl sulfates, alkyl diglycol ether sulfates, alcohol sulfates, alkyl sulfonates, alkylaryl sulfonates, aryl sulfonates, lignin sulfonates, alkyl diphenyl ether disulfonates, polystyrene sulfonates, alkyl phosphates, alkylaryl phosphates, styrylaryl phosphates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylaryl ether sulfates, and polyoxyethylene alkyl ether phosphates. Examples include anionic surfactants such as polyoxyethylene alkylaryl phosphate salts and naphthalene sulfonic acid formalin condensate salts, and nonionic surfactants such as sorbitan fatty acid esters, glycerin fatty acid esters, fatty acid polyglycerides, fatty acid alcohol polyglycol ethers, acetylene glycol, acetylene alcohol, oxyalkylene block polymers, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene styrylaryl ethers, polyoxyethylene glycol alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene hydrogenated castor oil, and polyoxypropylene fatty acid esters.

[0037] Examples of binders and thickeners, though not limited to them, include dextrin, pregelatinized starch, sodium salt of carboxymethylcellulose, polycarboxylic acid polymers, polyvinylpyrrolidone, polyvinyl alcohol, sodium ligninsulfonate, calcium ligninsulfonate, sodium polyacrylate, gum arabic, sodium alginate, mannitol, sorbitol, bentonite-based minerals, polyacrylic acid and its derivatives, white carbon, and natural sugar derivatives (e.g., xanthan gum, guar gum, etc.).

[0038] Examples of antifreeze agents, though not limited to them, include ethylene glycol, diethylene glycol, propylene glycol, and glycerin.

[0039] Examples of preservatives, though not limited to them, include benzoic acid, sodium benzoate, methyl parahydroxybenzoate, butyl parahydroxybenzoate, isopropylmethylphenol, benzalkonium chloride, chlorhexidine hydrochloride, hydrogen peroxide, chlorhexidine gluconate, salicylic acid, sodium salicylate, zinc pyrithione, sorbic acid, potassium sorbate, dehydroacetic acid, sodium dehydroacetate, phenoxyethanol, isothiazolin derivatives such as 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, 2-bromo-2-nitropropane-1,3-diol, and salicylic acid derivatives.

[0040] Examples of defoaming agents include silicone-based defoaming agents, although these are not limited to any specific type.

[0041] The solid carriers, liquid carriers, binders, thickeners, surfactants, antifreezes, preservatives, and defoamers described above can be used individually or in appropriate combinations depending on the intended use.

[0042] These formulations can be used for various purposes by diluting them to an appropriate concentration as needed and spraying them on or directly applying them to pests or their habitats (plants, soil in which plants are grown, inside houses, and animal bodies, etc.).

[0043] The dosage of the compound of formula (1) of the present invention can be varied over a wide range depending on the type of compound, the type of target plant, the time of application, the location of application, the properties of the desired effect, etc. However, as a general guideline, an example can be given of about 0.01 to 100 g, preferably about 0.1 to 10 g, of the active compound per are.

[0044] The pest control method of the present invention is carried out by applying an effective amount of the compound of the present invention directly to the pest and / or to the habitat of the pest. Examples of habitats for pests include plants, soil in which plants are cultivated, inside houses, and animal bodies.

[0045] Methods for applying an effective amount of the compound of the present invention to plants or the soil in which plants are cultivated include, for example, applying an effective amount of the compound of the present invention to the stems and leaves, flower stalks, seedlings or ears of plants; applying an effective amount of the compound of the present invention to seeds or bulbs such as seed potatoes through seed disinfection, seed soaking, or seed coating; and applying an effective amount of the compound of the present invention to the soil before or after planting plants.

[0046] Methods for applying an effective amount of the compound of the present invention to the stems, leaves, flower stalks, seedlings, or ears of plants include, specifically, applying an effective amount of the compound of the present invention or the pest control agent of the present invention to the surface of the plant, such as by foliar spraying or trunk spraying; spraying an effective amount of the compound of the present invention onto the flower stalks or the entire plant during the flowering period, including before, during, and after flowering; and, in the case of grains, spraying an effective amount of the compound of the present invention onto the ears or the entire plant at the heading stage.

[0047] Furthermore, methods for controlling harmful organisms by applying an effective amount of the compound of the present invention to the soil before or after planting plants include, for example, a method of directly controlling harmful organisms by applying an effective amount of the compound of the present invention to the rhizosphere of crops that are to be protected from damage such as feeding by harmful organisms, or a method of controlling harmful organisms that feed on plants by allowing an effective amount of the compound of the present invention to permeate and move into the plant body from the roots or other parts.

[0048] Methods for applying an effective amount of the compound of the present invention to the soil before or after planting plants include, for example, planting hole treatment (spraying in planting holes, mixing into planting hole treatment soil), base treatment (spraying around the base of the plant, mixing into the base of the plant soil, drenching around the base of the plant, base treatment in the latter half of the seedling stage), furrow treatment (spraying in planting furrows, mixing into planting furrow soil), furrowing treatment (spraying in furrows, mixing into furrow soil, spraying in furrows during the growing season), furrowing treatment at sowing (spraying in furrows at sowing, mixing into furrows at sowing), overall treatment (spraying in the overall soil, mixing into the overall soil), side-dressing treatment, water surface treatment (application to the water surface, application to the water surface after flooding), and other soil application treatments (foliar application of granular material during the growing season, application under the tree canopy or around the main trunk, application to the soil surface, mixing into the soil surface, sowing Examples of treatments include hole application, surface application on ridges, interplant application), other drenching treatments (soil drenching, seedling stage drenching, chemical injection treatment, base drenching, chemical drip irrigation, chemigation), seedling tray treatments (seedling tray application, seedling tray drenching, seedling tray watering), seedling tray treatments (seedling tray application, seedling tray drenching, seedling tray watering), seedling bed treatments (seedling bed application, seedling bed drenching, watered seedling bed application, seedling soaking), bed soil mixing treatments (bed soil mixing, bed soil mixing before sowing, application before covering with soil at sowing, application after covering with soil at sowing, covering with soil mixing), and other treatments (growing soil mixing, tilling, topsoil mixing, soil mixing at rainwater drainage points, planting location treatment, granular flower cluster application, paste fertilizer mixing).

[0049] In the process of applying the compound to seeds or bulbs, "seeds" refers to plant seeds before sowing in soil or a growing medium, and "bulbs" refers to plant bulbs, corms, tubers, rhizomes, stem fragments, seed potatoes, or tuberous roots before planting in soil or a growing medium. Methods for controlling pests by applying an effective amount of the compound of the present invention to seeds or bulbs include, for example, a method of directly applying an effective amount of the compound of the present invention to the seeds or bulbs of a plant that you want to protect from damage such as feeding by pests to control pests; a method of applying an effective amount of the compound of the present invention near the seeds or bulbs to control pests that feed on seeds, etc.; or a method of allowing an effective amount of the compound of the present invention to permeate and move from the seeds or bulbs into the plant body to control pests that feed on plants. Methods for applying an effective amount of the compound of the present invention to seeds or bulbs include, for example, spraying, coating, dipping, impregnation, coating, film coating, and pellet coating. These methods can be used to prepare seeds or bulbs that retain an effective amount of the compound of the present invention on their surface and / or internally.

[0050] When the compound of the present invention is applied to seeds or bulbs, the effective amount of the compound of the present invention is usually 0.001 to 100 g, preferably 0.02 to 20 g, per 1 kg of seeds or bulbs.

[0051] The following are examples of plants in which the compounds and pest control agents of the present invention can be used: Agricultural crops: corn, rice, wheat, barley, rye, oats, sorghum, cotton, soybeans, peanuts, buckwheat, sugar beets, rapeseed, sunflowers, sugarcane, tobacco, etc. Vegetables: Solanaceae vegetables (eggplant, tomato, bell pepper, chili pepper, potato, etc.), Cucurbitaceae vegetables (cucumber, pumpkin, zucchini, watermelon, melon, etc.), Brassicaceae vegetables (radish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, mustard greens, broccoli, cauliflower, etc.), Asteraceae vegetables (burdock, garland chrysanthemum, artichoke, lettuce, etc.), Liliaceae vegetables (leek, onion, garlic, asparagus), Apiaceae vegetables (carrot, parsley, celery, angelica tree, etc.), Amaranthaceae vegetables (spinach, Swiss chard, etc.), Lamiaceae vegetables (perilla, mint, basil, etc.), strawberries, sweet potatoes, yams, taro, etc. Fruit trees: Pome fruits (apples, European pears, Japanese pears, quince, marzipan, etc.), drupes (peaches, plums, nectarines, apricots, cherries, prunes, etc.), citrus fruits (Unshu mandarins, oranges, lemons, limes, grapefruit, etc.), nuts (chestnuts, walnuts, hazelnuts, almonds, pistachios, cashews, macadamia nuts, etc.), berries (blueberries, cranberries, blackberries, raspberries, etc.), grapes, persimmons, olives, loquats, bananas, coffee, dates, coconuts, oil palms, etc.; Trees other than fruit trees: Tea, mulberry, flowering trees (azalea, camellia, hydrangea, sasanqua, Japanese star anise, cherry, tulip tree, crape myrtle, osmanthus, etc.), street trees (ash, birch, dogwood, eucalyptus, ginkgo, lilac, maple, oak, poplar, Judas tree, sweetgum, plane tree, zelkova, Japanese cypress, fir, hemlock, juniper, pine, spruce, yew, elm, horse chestnut, etc.), coralberry, Japanese yew, cedar, cypress, croton, Japanese spindle tree, photinia, etc.;Lawns: Zoysia grasses (Zoysia japonica, Zoysia japonica, etc.), Bermuda grasses (Zoysia japonica, etc.), Bentgrasses (Poa annua, Poa arvensis, Poa crus-galli, etc.), Bluegrasses (Poa annua, Poa maximowiczii, Poa japonica, etc.), Fescues (Poa annua, Poa crus-galli, Poa japonica, etc.), Ryegrasses (Ryegrass, Ryegrass, etc.), Timothy grass, Oriental grass, etc. Others: Flowering plants (roses, carnations, chrysanthemums, lisianthus, baby's breath, gerberas, marigolds, salvias, petunias, verbenas, tulips, asters, gentians, lilies, pansies, cyclamen, orchids, lilies of the valley, lavender, stocks, ornamental cabbages, primroses, poinsettias, gladiolus, cattleyas, daisies, cymbidiums, begonias, etc.), biofuel plants (jatropha, safflower, thuja species, switchgrass, miscanthus, reeds, giant bamboo, kenaf, cassava, willow, etc.), ornamental plants, etc.

[0052] The aforementioned plants include genetically modified plants.

[0053] The present invention will be described in more detail below with reference to manufacturing examples, formulation examples, and test examples, but the present invention is not limited to these examples. <Manufacturing Examples>

[0054] Preparation Example 1-1. Method for preparing methyl 4-bromo-2-chlorobenzeneacetate 100.4 g (394.3 mmol) of 4-bromo-2-chlorobenzeneacetic acid was dissolved in methanol (800 mL) and stirred at room temperature. 40.7 g (394.3 mmol) of concentrated sulfuric acid was added and refluxed for 7 hours. After the reaction was complete, the reaction mixture was cooled on ice, and 400 mL of saturated sodium bicarbonate aqueous solution was carefully added dropwise. The solvent was removed by vacuum distillation and extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over sodium sulfate. The solvent was then removed by vacuum distillation to obtain a pale yellowish-brown oil (99.7 g), which was used in the next reaction without purification.

[0055] Preparation Example 1-2. Method for producing 4-bromo-2-chloro-α-(hydroxyimino)benzenemethyl acetate. 89.2 g (338.4 mmol) of crude 4-bromo-2-chlorobenzenemethyl acetate obtained in Preparation Example 1-1 was dissolved in tetrahydrofuran (700 mL) and stirred at room temperature. 50.1 g (406.1 mmol) of isoamyl nitrite dissolved in tetrahydrofuran (300 mL) and sodium methoxide (5M methanol solution, 507.6 mmol) were added, and the mixture was stirred under a nitrogen atmosphere for 1 day. After the reaction was complete, the solvent was removed by vacuum distillation, and 10% hydrochloric acid was added dropwise until the precipitated solid was completely dissolved, followed by extraction with ethyl acetate. The organic layer was washed with water and saturated brine, dried over sodium sulfate, and the solvent was removed by vacuum distillation to obtain a yellow-orange oil (97.1 g). This oil was used in the next reaction without purification.

[0056] Preparation Example 1-3. Method for producing β-amino-4-bromo-2-chlorobenzeneethanol. 97.1 g (316.7 mmol) of crude 4-bromo-2-chloro-α-(hydroxyimino)benzenemethyl acetate obtained in Preparation Example 1-2 was dissolved in tetrahydrofuran (300 mL) and stirred under ice cooling. 40.4 g (1013.4 mmol) of sodium borohydride was added, and then 129.9 g (506.7 mmol) of iodine dissolved in tetrahydrofuran (300 mL) was slowly added dropwise, and the mixture was refluxed for 5 hours. The reaction mixture was cooled on ice, and water (150 mL) was carefully added dropwise, followed by the addition of 49.0 g (1140.1 mmol) of sodium hydroxide and water (150 mL), and the mixture was refluxed for a further 5 hours. After removing the solvent under reduced pressure, the mixture was extracted with ethyl acetate and dried with sodium sulfate. The solvent was then removed under reduced pressure, and the resulting solid was washed with diisopropyl ether to obtain the target product (39.2 g) as a yellowish-white solid.

[0057] Preparation Example 1-4. Method for producing N-{1-(4-bromo-2-chlorophenyl)-2-[(methylsulfonyl)oxy]ethyl}-2,6-difluorobenzamide. 39.2 g (156.5 mmol) of β-amino-4-bromo-2-chlorobenzeneethanol obtained in Preparation Example 1-3 was dissolved in tetrahydrofuran (300 mL), and 48.0 g (469.5 mmol) of triethylamine was added and the mixture was stirred under ice cooling. 27.9 g (156.5 mmol) of 2,6-difluorobenzoyl chloride dissolved in tetrahydrofuran (70 mL) was slowly added dropwise and the mixture was stirred at room temperature for 1 hour. After the amidation was complete, the reaction mixture was cooled on ice and 21.7 g (187.8 mmol) of methanesulfonyl chloride dissolved in tetrahydrofuran (70 mL) was slowly added dropwise and the mixture was stirred at room temperature for 1 hour. After the reaction was complete, the precipitated solid was filtered off and washed with tetrahydrofuran. The filtrate was concentrated under reduced pressure to obtain a pale yellowish-brown oil (73.4 g), which was used in the next reaction without further purification.

[0058] Preparation Example 1-5. Method for producing 4-(4-bromo-2-chlorophenyl)-2-(2,6-difluorophenyl)-4,5-dihydroxazole Crude N-{1-(4-bromo-2-chlorophenyl)-2-[(methylsulfonyl)oxy]ethyl}-2,6-difluorobenzamide 73.4 g (156.5 mmol) obtained in Preparation Example 1-4 was dissolved in methanol (300 mL), and 16.8 g (391.3 mmol) of sodium hydroxide was added and the mixture was stirred at room temperature for 1 hour. After the reaction was complete, water was added to the reaction mixture and the solvent was removed by vacuum distillation and extracted with ethyl acetate. The organic layer was washed with water and saturated brine and dried over sodium sulfate. The solvent was then removed by vacuum distillation and the resulting crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 4 / 1) to obtain the target product (34.1 g) as a white solid.

[0059] Preparation Example 1-6.5-{3-chloro-4-[2-(2,6-difluorophenyl)-4,5-dihydro-4-oxazolyl]phenyl}-2-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]pyridine (Compound 14) 140.6 g (377.5 mmol) of 4-(4-bromo-2-chlorophenyl)-2-(2,6-difluorophenyl)-4,5-dihydroxazole obtained in Preparation Examples 1-5, 211.2 g (566.3 mmol) of 2-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine, 208.7 g (1510.0 mmol) of potassium carbonate, and 13.8 g (18.9 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (C) were dissolved in a mixed solvent of 1,2-dimethoxyethane (1020 mL) and water (210 mL) and refluxed under a nitrogen atmosphere. After the reaction was complete, water was added to the reaction mixture and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over sodium sulfate, and the solvent was removed under reduced pressure. The resulting crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 4 / 1) to obtain the target product (230.1 g) as a light brown solid.

[0060] Preparation Example 2-1. Method of preparing ethyl acetate 2-fluoro-4-iodo-α-oxobenzene A mixture of 181.4 g (1324.3 mmol) of aluminum chloride and dichloromethane (1.1 L) was mixed with 168.6 g (1214.0 mmol) of ethyl chloroglyoxylate at room temperature while stirring. After stirring at room temperature for 1 hour, 250.0 g (1103.6 mmol) of 1-fluoro-3-iodobenzene was added and the mixture was stirred at room temperature for 1 day. After the reaction was complete, the reaction mixture was carefully poured onto ice and extracted with ethyl acetate. The organic layer was washed with saturated sodium thiosulfate aqueous solution and saline solution, dried over sodium sulfate, and the solvent was removed by vacuum distillation. The resulting pale yellowish-brown solid (298.9 g) was used in the next reaction without purification.

[0061] Preparation Example 2-2. Method for producing 2-fluoro-4-iodo-α-(hydroxyimino)benzene ethyl acetate. 298.9 g (927.9 mmol) of crude 2-fluoro-4-iodo-α-oxobenzene ethyl acetate obtained in Preparation Example 2-1 was dissolved in ethanol (900 mL) and stirred at room temperature. 78.2 g (1113.5 mol) of hydroxylamine hydrochloride was added and refluxed for 6 hours. After the reaction was complete, the solvent was removed by vacuum distillation, and the solution was diluted with ethyl acetate. The diluted solution was washed with water and saturated saline solution, dried over sodium sulfate, and the solvent was removed by vacuum distillation. The crude product obtained was purified by silica gel column chromatography (hexane / ethyl acetate = 3 / 1) to obtain the target product (191.9 g) as a white solid.

[0062] Preparation Example 3-1. Method of 2-(4-bromo-2-chlorophenyl)oxirane Under stirring, 36.3 g (460.0 mmol) of dimethyl sulfoxide was heated to 100°C, and 44.4 g (345.0 mmol) of dimethyl sulfate was added and the mixture was stirred for 2 hours to generate trimethylsulfoxonium ions. This solution was dissolved in toluene (177 mL), and 1.5 g (4.7 mmol) of tetrabutylammonium bromide, 50.1 g (759.0 mmol) of potassium hydroxide, and 50.5 g (230.0 mmol) of 4-bromo-2-chlorobenzaldehyde were added and the mixture was stirred at room temperature. After the reaction was complete, the reaction mixture was washed with water and dried over sodium sulfate, and the solvent was removed by distillation under reduced pressure. The crude product obtained was purified by silica gel column chromatography (hexane / ethyl acetate = 95 / 5) to obtain the target product (11.3 g) as a yellow liquid.

[0063] Preparation Example 3-2. Method for producing β-azido-4-bromo-2-chlorobenzeneethanol. 11.2 g (48.0 mmol) of 2-(4-bromo-2-chlorophenyl)oxirane obtained in Preparation Example 3-1 was dissolved in water (96 mL), and 10.4 g (144.0 mmol) of sodium azide was added and the mixture was heated at 80°C. After the reaction was complete, the mixture was extracted with diisopropyl ether, the organic layer was washed with water and saturated saline solution, and dried with sodium sulfate. The solvent was then removed by vacuum distillation to obtain the target product (11.5 g) as a pale yellow solid.

[0064] Preparation Example 3-3. Method for producing β-amino-4-bromo-2-chlorobenzeneethanol 11.5 g (41.6 mmol) of β-azide-4-bromo-2-chlorobenzeneethanol obtained in Preparation Example 3-2 was dissolved in tetrahydrofuran (240 mL), and 19.9 g (72.0 mmol) of triphenylphosphine and 17.3 g (960 mmol) of water were added and the mixture was heated at 70°C. After the reaction was complete, the solvent was removed by distillation under reduced pressure, methanol (173 mL) and 2 M hydrochloric acid (34.6 mL) were added, and the mixture was stirred at room temperature for 2 hours. The aqueous layer was separated and organic impurities were removed by extraction with chloroform, and 9.6 g of sodium hydroxide was added to the aqueous layer and the mixture was stirred at room temperature for 30 minutes, after which it was extracted with chloroform. The organic layer was dried over sodium sulfate, and the solvent was removed by distillation under reduced pressure to obtain the target product (9.5 g) as a pale yellow solid.

[0065] Preparation Example 4-1. Method for preparing 6-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-3-pyridineamine 47.1 g (500.4 mmol) of 3-aminopyridine, 160.0 g (1501.2 mmol) of sodium carbonate, and 10.9 g (32.0 mmol) of tetrabutylammonium bisulfate were dissolved in ethyl acetate / water = 2 / 3 (1 L), and 177.6 g (600.5 mmol) of 1,1,1,2,3,3,3-heptafluoro-2-iodopropane was added under stirring at room temperature. The reaction mixture was heated to 50°C, and 104.5 g (600.5 mmol) of sodium dithionite was added in small amounts over 30 minutes. After the reaction was complete, the reaction mixture was cooled to room temperature, the organic layer was separated, washed with water and saturated brine, dried over sodium sulfate, and the solvent was removed under reduced pressure. The resulting crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 2 / 1) to obtain the target product (38.2 g) as a light brown liquid.

[0066] Preparation Example 4-2. Method for producing 2-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine 219.3 g (836.6 mmol) of 6-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-3-pyridineamine obtained in Preparation Example 4-1 and 223.1 g (878.4 mmol) of bis(pinacolato)diborone were dissolved in acetonitrile (840 mL) and stirred at room temperature. 5.4 g (16.7 mmol) of 75% benzoyl peroxide was added. 143.8 g (1254.9 mmol) of 90% tert-butyl nitrite dissolved in acetonitrile (420 mL) was added and stirred for 1 day. After the reaction was complete, water was added to the reaction mixture to remove the solvent under reduced pressure, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over sodium sulfate, and the solvent was removed under reduced pressure. The resulting crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 9 / 1) to obtain the target product (303.0 g) as a light brown solid.

[0067] Preparation Example 5-1. Method for preparing 5-bromo-2(1H)-pyridinion 8.7 g (50.0 mmol) of 5-bromo-2(1H)-pyridinone and 10.11 g (25.0 mmol) of Lawson's reagent were dissolved in toluene (250 mL) and refluxed under a nitrogen atmosphere for 1 hour. After the reaction was complete, the reaction mixture was cooled to room temperature, the precipitated solid was filtered off, and the resulting yellow solid (8.8 g) was dried under vacuum and used in the next reaction without purification.

[0068] Preparation Example 5-2. Method for preparing 5-bromo-2-[(1,1,2,2,3,3,4,4,4-nonafluorobutyl)thio]pyridine 5.7 g (50.8 mmol) of 97% tert-butoxypotassium and tetrahydrofuran (45 mL) were stirred at room temperature, and 8.8 g (46.2 mmol) of crude 5-bromo-2(1H)-pyridinethion obtained in Preparation Example 5-1 was added thereto. After stirring the reaction mixture at 50°C for 1 hour, the solvent was removed by distillation under reduced pressure, and the resulting residue was dissolved in dimethyl sulfoxide (45 mL). 17.6 g (50.8 mmol) of nonafluorobutyl iodide was added dropwise while stirring at room temperature. After the reaction was complete, water was added to the reaction solution and extracted with a hexane / ethyl acetate = 1 / 1 mixed solvent. The organic layer was washed with water and dried over sodium sulfate. The solvent was then removed under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (hexane) to obtain the target product (10.0 g) as a colorless solid.

[0069] Preparation Example 5-3. Method for preparing 2-[(1,1,2,2,3,3,4,4,4-nonafluorobutyl)thio]-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine] 10.0 g (24.6 mmol) of 5-bromo-2-[(1,1,2,2,3,3,4,4,4-nonafluorobutyl)thio]pyridine obtained in Preparation Example 5-2, 6.9 g (27.1 mmol) of bis(pinacolato)diborone, 0.5 g (0.7 mmol) of 1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (Ц), and 7.2 g (73.8 mmol) of potassium acetate were dissolved in N,N-dimethylformamide (50 mL) and stirred at 90°C under a nitrogen atmosphere. After the reaction was complete, the reaction mixture was cooled to room temperature, water (50 mL) was added, and the mixture was filtered using Celite. The filtrate was washed with water and dried over sodium sulfate. The solvent was then removed by reduced pressure, and the resulting crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 9 / 1) to obtain the target product (6.6 g) as a light brown solid.

[0070] The example compounds listed in Table 1 below were prepared in the same manner as described above, or obtained in the same manner as described above.

[0071]

[0072]

[0073] <Examples of Formulations>

[0074] 1. A powder is obtained by mixing 10 parts by weight of the powder compound (1) with 90 parts by weight of talc and finely grinding it with a hammer mill.

[0075] 2. A wettable powder is obtained by mixing 10 parts by weight of the compound of wettable powder formula (1), 22.5 parts by weight of polyoxyethylene alkylaryl ether sulfate, and 67.5 parts by weight of clay, and then finely grinding this mixture with a hammer mill.

[0076] 3. Compound of flowable formulation (1) A flowable formulation is obtained by mixing 10 parts by weight of polyoxyethylene allylphenyl ether phosphate, 4 parts by weight of bentonite, 5 parts by weight of propylene glycol, 6 parts by weight of silicone-based defoaming agent, 0.5 parts by weight of 1,2-benzoisothiazolin-3-one, 0.2 parts by weight of water, and grinding the mixture using a wet grinder.

[0077] 4. An emulsion is obtained by mixing 10 parts by weight of the emulsion formula (1) compound, 15 parts by weight of polyoxyethylene tristilphenyl ether, and 75 parts by weight of xylene.

[0078] 5. Compound of granular formulation (1): Mix 5 parts by weight of calcium ligninsulfonate, 3 parts by weight of polycarboxylate, and 89 parts by weight of calcium carbonate. Add water and knead, then extrude to granulate. After drying and sizing, granules are obtained. <Example of biological test>

[0079] Test Example 1-1 Existing Agent-Susceptible Diamondback Moth Control Test Leaf discs with a diameter of 5.0 cm were prepared from pot-grown radishes, and the active compound diluted to 1 ppm was sprayed on them (0.05% tween20 added). After air drying, first-instar larvae were released onto them. Then, they were left in a constant temperature room at 25°C (16 hours light period - 8 hours dark period). After 4 days of release, the viability of the insects was observed, and the mortality rate was calculated according to the following formula: Mortality rate (%) = {Number of dead insects / (Number of surviving insects + Number of dead insects)} × 100 The results are shown in Table 2. The compound of the present invention and comparative controls 1, 2, 3, and 4 showed high control performance. Control agent 1 (described in Japanese Patent Publication No. 2000-503013) Control agent 2 (described in Japanese Patent Publication No. 2002-518389) Control agent 3 (described in Japanese Patent Publication No. 2002-518389) Control agent 4 (described in Japanese Patent Publication No. 2002-518389)

[0080] Test Example 1-2 Control Test for Existing Agent-Resistant Diamondback Moth Leaf discs with a diameter of 5.0 cm were prepared from pot-grown radishes, and an active compound diluted to 1 ppm was sprayed on them (with the addition of 0.05% tween20). After air drying, diamondback moth first-instar larvae resistant to diamide insecticides and IGR insecticides were released onto them. Subsequently, these were left in a constant temperature chamber at 25°C (16 hours light period - 8 hours dark period). After 4 days of release, the survival of the insects was observed, and the mortality rate was calculated according to the following formula: Mortality rate (%) = {Number of dead insects / (Number of surviving insects + Number of dead insects)} × 100 The results are shown in Table 2. The compound of the present invention showed high control performance. On the other hand, comparative controls 1, 2, 3, and 4 had mortality rates of 30% or less, indicating insufficient control performance.

[0081]

[0082] Test Example 1-3 Control Test for Citrus Thrips Susceptible to Existing Agents Circular leaf discs with a diameter of 3.0 cm were prepared from pot-grown green beans, and an active compound diluted to a predetermined concentration was sprayed onto them (0.05% tween20 added). After air drying, first-instar larvae were released onto them. Subsequently, these were left in a constant temperature room at 25°C (16 hours light period - 8 hours dark period). After 4 days of release, the survival of the insects was observed, and the mortality rate was calculated according to the following formula: Mortality rate (%) = {Number of dead insects / (Number of surviving insects + Number of dead insects)} × 100 The results are shown in Table 3. The compound of the present invention and comparative controls 1, 2, 3, and 4 showed high control performance.

[0083] Test Example 1-4 Control Test for Citrus Thrips Resistant to Existing Insecticides Circular leaf discs with a diameter of 3.0 cm were prepared from pot-grown green beans, and an active compound diluted to a predetermined concentration was sprayed onto them (0.05% tween20 added). After air drying, first-instar larvae of the citrus thrips, which are resistant to IGR insecticides, neonicotinoid insecticides, organophosphate insecticides, and synthetic pyrethroid insecticides, were released onto them. Subsequently, these were left in a constant temperature chamber at 25°C (16 hours light period - 8 hours dark period). After 4 days of release, the viability of the insects was observed, and the mortality rate was calculated according to the following formula: Mortality rate (%) = {Number of dead insects / (Number of surviving insects + Number of dead insects)} × 100 The results are shown in Table 3. The compound of the present invention showed high control performance. On the other hand, control groups 1, 2, 3, and 4 had mortality rates of 30% or less, indicating insufficient pest control performance.

[0084]

[0085] Test Example 1-5 Control Test for Existing Agent-Susceptible Spider Mites Leaf discs with a diameter of 3.0 cm were prepared from pot-grown green beans and inoculated with adult female mites. After 24 hours, the adult female mites were removed, the laid eggs were counted, and the active compound diluted to 100 ppm was sprayed on them (0.05% tween20 added). After air drying, the discs were left in a constant temperature room at 25°C (16 hours light - 8 hours dark). After 7 days of release, the viability of the mites was observed, and the mortality rate was calculated according to the following formula: Mortality rate (%) = {(Number of unhatched eggs + Number of dead mites) / Number of laid eggs} × 100 The results are shown in Table 4. The compound of the present invention and comparative controls 1, 2, 3, and 4 showed high control performance.

[0086] Test Example 1-6 Control Test for Existing Agent-Resistant Spider Mites Leaf discs with a diameter of 3.0 cm were prepared from pot-grown green beans and inoculated with adult female spider mites resistant to IGR-type acaricides, mitochondrial electron transport chain complex I, mitochondrial electron transport chain complex 3 inhibitors, organophosphate acaricides, and synthetic pyrethroid acaricides. After 24 hours, the adult females were removed, the laid eggs were counted, and the active compound diluted to 100 ppm was sprayed on them (with the addition of 0.05% tween20). After air drying, the discs were left in a constant temperature room at 25°C (16 hours light - 8 hours dark). After 7 days of release, the viability of the insects was observed, and the mortality rate was calculated according to the following formula: Mortality rate (%) = {(Number of unhatched eggs + Number of dead insects) / Number of laid eggs} × 100 The results are shown in Table 4. The compound of the present invention showed high control performance. On the other hand, control groups 1, 2, 3, and 4 had a mortality rate of less than 30% even at 100 ppm, indicating insufficient pest control performance.

[0087]

[0088] Test Example 1-7 Control Test for Existing Agent-Resistant Rhinogobius rhizome Two leaf discs with a diameter of 3.0 cm were prepared from pot-grown radishes, and the active compound diluted to 1 ppm was sprayed on them (0.05% tween20 added). After air drying, third-instar larvae of Rhinogobius rhizome, which are resistant to diamide insecticides and IGRs, were released onto them. Then, they were left in a constant temperature room at 25°C (16 hours light - 8 hours dark). Six days after release, the survival of the insects was observed, and the mortality rate was calculated according to the following formula: Mortality rate (%) = {Number of dead insects / (Number of surviving insects + Number of dead insects)} × 100 The results are shown in Table 5. The compound of the present invention showed high control performance. On the other hand, comparative controls 1, 2, 3, and 4 had mortality rates of 30% or less, indicating insufficient control performance.

[0089]

[0090] The compounds of the present invention have control efficacy against harmful organisms and are useful as active ingredients in pest control agents.

Claims

1. Formula (1): [In the formula, R １ R represents a C1-C6 perfluoroalkyl group or a C1-C6 perfluoroalkylthio group. ２ represents a halogen atom. A substituted pyridylphenyloxazoline derivative compound represented by ].

2. R ２ The compound according to claim 1, wherein is a fluorine atom or a chlorine atom.

3. R １ The compound according to claim 1, wherein is a C1-C4 perfluoroalkyl group or a C3-C4 perfluoroalkylthio group.

4. R １ The compound according to claim 3, wherein is a C3-C4 perfluoroalkyl group or a C3-C4 perfluoroalkylthio group.

5. R １ The compound according to claim 1, wherein the compound is a C1-C6 perfluoroalkyl group.

6. R １ The compound according to claim 5, wherein is a C3-C4 perfluoroalkyl group.

7. A pest control agent containing a compound and an auxiliary agent according to any one of claims 1 to 6.

8. A method for controlling pests, comprising applying an effective amount of the compound described in any one of claims 1 to 6.

9. The method according to claim 8, comprising applying an effective amount of any compound according to claim 1 to claim 6 to a pest or a plant inhabited by a pest or to soil in which the plant is cultivated.

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