WO2018186440A1 - Nouveau dérivé de 1-phénylpipéridine et agent pharmaceutique agricole/horticole le contenant en tant que composant actif - Google Patents

Nouveau dérivé de 1-phénylpipéridine et agent pharmaceutique agricole/horticole le contenant en tant que composant actif Download PDF

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WO2018186440A1
WO2018186440A1 PCT/JP2018/014409 JP2018014409W WO2018186440A1 WO 2018186440 A1 WO2018186440 A1 WO 2018186440A1 JP 2018014409 W JP2018014409 W JP 2018014409W WO 2018186440 A1 WO2018186440 A1 WO 2018186440A1
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group
formula
haloalkyl
alkyl group
following formula
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PCT/JP2018/014409
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Japanese (ja)
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一秋 小山
黒瀬　裕
恒一 荒木
響 八田
麻紀子 山口
福地　俊樹
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アグロカネショウ株式会社
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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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings

Definitions

  • the present invention relates to a novel 1-phenylpiperidine derivative, an agricultural and horticultural agent containing the compound as an active ingredient, particularly an agricultural and horticultural pest control agent, a tick control agent or a nematode control agent, and a method of using the same.
  • Patent Document 1 describes that 1-phenylpiperidine derivatives are useful as insecticides for animals.
  • Patent Document 1 does not disclose a compound in which a sulfur-containing substituent as in the present invention is directly introduced as a substituent at the 3-position of the phenyl group of a 1-phenylpiperidine derivative.
  • Patent Documents 2 to 3 the following compounds are disclosed as related compounds of the compound of the present invention.
  • Patent Documents 2 to 3 these compounds disclosed in Patent Documents 2 to 3 are all different in chemical structure from the compound of the present invention.
  • a 1-phenylpiperidine derivative represented by the following formula (I), which is a novel compound not described in any literature, is an agricultural and horticultural agent, particularly agricultural
  • the present invention has been completed by finding it useful as a horticultural pest control agent, a tick control agent or a nematode control agent.
  • the present invention provides the following formula (1), [Where R is a C 1-6 alkyl group, a C 1-6 haloalkyl group, a C 2-6 alkenyl group, a C 2-6 haloalkenyl group, a C 2-6 alkynyl group, a C 2-6 haloalkynyl group, a C 3- 6 cycloalkyl represents a C 1-6 alkyl group or C 3-6 halocycloalkyl C 1-6 alkyl group, X is a C 1-6 alkyl group, C 1-6 haloalkyl group, C 3-6 cycloalkyl group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 2-6 haloalkenyl group, C 2- 6 haloalkynyl group, C 1-6 alkoxy, C 1-6 haloalkoxy group, C 3-6 halocycloalkyl group, C 1-6 alkoxymethyl group, C 1-6 1-6 al
  • the compound of the present invention has an excellent effect as an agricultural and horticultural agent, particularly as an agricultural and horticultural pest control agent, tick control agent, nematode control agent or disease control agent. It is also effective against pests parasitizing pets such as dogs and cats or livestock such as cattle and sheep.
  • the halogen atom means a chlorine atom, a bromine atom, an iodine atom or a fluorine atom, and a C 1-6 alkyl group (a group containing this group as a substituent, For example, the same applies to a C 1-6 alkyl group in the case of a C 3-6 cycloalkyl C 1-6 alkyl group, etc.
  • a methyl group for example, a methyl group, an ethyl group, n -Propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group,
  • C 1-6 haloalkyl group represents a linear or branched alkyl group having 1 to 6 carbon atoms substituted with one or more halogen atoms which may be the same or different, and includes, for example, a fluoromethyl group, chloro Methyl group, difluoromethyl group, trifluoromethyl group, chlorodifluoromethyl group, bromodifluoromethyl group, dichlorofluoromethyl group, 1-fluoroethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2 -Iodoethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, pentafluoroethyl group, 2,2-difluoroethyl group, 1-fluoroisopropyl group, 3-fluoropropyl group, 3 -Chloropropyl group, 3-bromopropy
  • Examples of the C 2-6 alkenyl group include vinyl group, allyl group, isopropenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1,1-dimethyl-2-propenyl group, 1-ethyl-2-propenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-hexenyl group, 3- Carbon having at least one double bond at any position such as hexenyl group, 4-hexenyl group, 5-hexenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, etc. Examples thereof include linear or branched alkenyl groups having 2 to 6.
  • Examples of the C 2-6 haloalkenyl group include 1-fluorovinyl group, 2-fluorovinyl group, 2,2-difluorovinyl group, 3-chloro-2-propenyl group, 3,3-difluoro-2-allyl group, 3,3-dichloro-2-allyl group, 4,4,4-trifluoro-2-butenyl group, 4,4,4-trifluoro-3-butenyl group, 5-chloro-3-pentenyl group, 6- Examples thereof include a linear or branched alkenyl group having 2 to 6 carbon atoms and substituted with 1 to 9 halogen atoms having at least one double bond at an arbitrary position such as a fluoro-2-hexenyl group.
  • Examples of the C 2-6 alkynyl group include ethynyl group, 2-propynyl group, 1-methyl-2-propynyl group, 1,1-dimethyl-2-propynyl group, 1-butynyl group, 2-butynyl group, 3 -Butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 1,1-dimethyl-2- 2 to 6 carbon atoms having at least one triple bond at an arbitrary position such as a butynyl group, 1,1-dimethyl-3-butynyl group, 1-methyl-3-pentynyl group, 1-methyl-4-pentynyl group, etc.
  • a linear or branched alkynyl group is mentioned.
  • C 2-6 haloalkynyl group includes fluoroethynyl group, 4,4,4-trifluoro-2-butynyl group, 5,5,5-trifluoro-3-pentynyl group, 1-methyl-3,3, Substituted with 1 to 9 halogen atoms having at least one triple bond at any position such as 3-trifluoro-2-butynyl group, 1-methyl-5,5,5-trifluoro-2-pentynyl group, etc. And a straight or branched alkynyl group having 2 to 6 carbon atoms.
  • Examples of the C 3-6 cycloalkyl group include cyclic cycloalkyl groups having 3 to 6 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
  • Examples of the C 1-6 alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a cyclopropyloxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, and an n-pentoxy group.
  • a linear or branched alkoxy group having 1 to 6 carbon atoms such as an n-hexyloxy group.
  • Examples of the C 1-6 haloalkoxy group include a fluoromethoxy group, a dichloromethoxy group, a trichloromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a chlorodifluoromethoxy group, a bromodifluoromethoxy group, a dichlorofluoromethoxy group, 1- Fluoroethoxy group, 2-fluoroethoxy group, 2-chloroethoxy group, 2-bromoethoxy group, 2-iodoethoxy group, 2,2,2-trifluoroethoxy group, 2,2,2-trichloroethoxy group, penta Fluoroethoxy group, 1-fluoroisopropoxy group, 3-fluoropropoxy group, 3-chloropropoxy group, 3-bromopropoxy group, 4-fluorobutoxy group, 4-chlorobutoxy group, etc., preferably 1-9 Linear or branched having 1 to 6 carbon atoms substituted with
  • Examples of the C 1-6 halocycloalkyl group include 1-fluorocyclopropyl, 2-fluorocyclopropyl, 2,2-difluorocyclopropyl, 2,2,3,3-tetrafluorocyclopropyl, 1-chlorocyclo Propyl, 2-chlorocyclopropyl, 2,2-dichlorocyclopropyl, 2,2,3,3-tetrachlorocyclopropyl, 2,2-dibromocyclopropyl, 1-fluorocyclobutyl, 2-fluorocyclobutyl, 3 -Fluorocyclobutyl, 3,3-difluorocyclobutyl, 3,3-dichlorocyclobutyl, 1-fluorocyclopentyl, 2-fluorocyclopentyl, 3-fluorocyclopentyl, 2,2-difluorocyclopentyl, 3,3-difluorocyclopentyl 2 , 2-dichlorocycl
  • Examples of the C 3-6 cycloalkyl C 1-6 alkyl group include cyclopropylmethyl, 2-cyclopropylethyl, 3-cyclopropylpropyl, 4-cyclopropylbutyl, 5-cyclopropylpentyl, and 6-cyclopropylhexyl. , Groups such as cyclobutylmethyl and cyclopentylmethyl.
  • Examples of the C 3 -C 6 halocycloalkyl C 1 -C 6 alkyl group include 1-fluorocyclopropylmethyl, 2-fluorocyclopropylmethyl, 2,2-difluorocyclopropylmethyl, 2-chlorocyclopropylmethyl, 2,2-dichlorocyclopropylmethyl, 2- (2,2-difluorocyclopropyl) ethyl, 2- (2,2-dichlorocyclopropyl) ethyl, 3- (2,2-difluorocyclopropyl) propyl, 4- (2,2-difluorocyclopropyl) butyl, 5- (2,2-dichlorocyclopropyl) pentyl, 6- (2,2-difluorocyclopropyl) hexyl, 2,2-difluorocyclobutylmethyl, 2,2- Dichlorocyclobutylmethyl, 3,3-difluorocyclopentylmethyl, 3,3-dichlor
  • Examples of the C 1-6 alkoxycarbonyl group include groups such as methoxycarbonyl, ethoxycarbonyl, n-propylcarbonyl, n-butylcarbonyl, n-pentylcarbonyl, n-hexylcarbonyl, i-propylcarbonyl group and the like.
  • Examples of the saturated heterocyclic ring containing oxygen include 1,3-dioxolane and 1,3-dioxane.
  • Examples of the saturated heterocyclic ring containing sulfur include 1,3-dithiane and 1,3-dithiolane.
  • Examples of the substituent in the benzyloxymethyl group which may be substituted include a halogen atom, a methyl group, an ethyl group, and a methoxy group.
  • Examples of the salt of the 1-phenylpiperidine derivative represented by the formula (I) of the present invention include, for example, hydrochlorides, inorganic acid salts such as sulfates, nitrates, phosphates, acetates, fumarates, Examples thereof include organic acid salts such as maleate, oxalate, methanesulfonate, benzenesulfonate, and p-toluenesulfonate.
  • the 1-phenylpiperidine derivative represented by the above formula (I) of the present invention may contain one or more asymmetric centers in the structural formula, and two or more optical isomers and diastereomers may be present.
  • the present invention includes all the optical isomers and a mixture in which they are contained in an arbitrary ratio.
  • the 1-phenylpiperidine derivative represented by the above formula (I) of the present invention may have two kinds of geometric isomers derived from a carbon-carbon double bond in its structural formula.
  • the invention also encompasses all geometric isomers and mixtures containing them in any proportion.
  • compounds in which R represents a C 1-6 alkyl group, a C 1-6 haloalkyl group or a C 3-8 cycloalkyl group are preferred, and further, a C 1-6 alkyl group, a C 1-6 Particularly preferred are compounds that exhibit a haloalkyl group.
  • compounds in which X represents a C 1-6 alkyl group, a C 1-6 alkoxymethyl group, a cyano group or a halogen group are preferred, and further, a C 1-3 alkyl group, a C 1-3 alkoxy A compound showing a methyl group, chlorine, bromine or cyano group is particularly preferred.
  • compounds in which Y represents a hydrogen atom, a halogen group or a C 1-6 alkyl group are preferred, and compounds showing a halogen group are particularly preferred.
  • compounds in which Z represents a C 1-6 haloalkyl group are preferable, and compounds that exhibit a fluoroalkyl group are particularly preferable.
  • compounds in which m is an integer of 1 to 3 are preferred, and compounds showing 1 are particularly preferred.
  • Reaction formula 1 [Wherein, X is a C 1-6 alkyl group, a C 1-6 haloalkyl group, a C 3-6 cycloalkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 2-6 haloalkenyl group, C 2-6 haloalkynyl group, C 1-6 alkoxy group, C 1-6 haloalkoxy group, C 3-6 halocycloalkyl group, C 1-6 alkoxymethyl group, C 1-6 haloalkoxymethyl group, substituted Benzyloxymethyl group, C 1-6 alkoxycarbonyl group, C 1-6 alkylcarbonyl group, hydroxymethyl group, formyl group, halogen
  • the 1-phenylpiperidine derivative represented by the formula (3) is obtained by combining the phenyl compound represented by the formula (5) and the piperidine compound represented by the formula (6) with a base. It can manufacture by making it react in an inert solvent in presence or absence of.
  • the solvent used in the reaction of the compound of formula (5) and the compound of formula (6) is not particularly limited as long as it is an inert solvent for the reaction, and is widely used. be able to.
  • solvents include alcohols such as methanol, ethanol, n-propanol, and iso-propanol, aliphatic or alicyclic hydrocarbon solvents such as hexane, cyclohexane, and heptane, benzene, chlorobenzene, toluene, Aromatic hydrocarbon solvents such as xylene, halogenated hydrocarbon solvents such as methylene chloride, 1,2-dichloroethane, chloroform, ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl acetate, ethyl acetate Ester solvents such as acetone, methyl ethyl ketone, amide solvents such as N, N-
  • inorganic bases and organic bases can be used as the base used in the reaction of the compound of the formula (5) and the compound of the formula (6).
  • the inorganic base include alkali metal carbonates such as sodium carbonate, potassium carbonate and sodium bicarbonate, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal hydrogen such as sodium hydride and potassium hydride.
  • the organic base include alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, and amines such as triethylamine and pyridine. These bases may be used alone or in combination of two or more.
  • Such a base can be used in an amount usually 1 to 100 equivalents, preferably 1 to 2 equivalents, relative to the phenyl compound represented by the formula (5).
  • the use ratio of the phenyl compound represented by the formula (5) and the piperidine compound represented by the formula (6) is such that the piperidine compound (6) is used in 1 to 2 moles relative to the phenyl compound (5). More preferably.
  • the reaction can be usually performed within a range from ⁇ 78 ° C. to the boiling point of the solvent used, and it is preferable to perform the reaction at room temperature to 100 ° C. Although the reaction time varies depending on the reaction temperature and the like and cannot be generally specified, the reaction is usually completed in about 0.5 to 24 hours.
  • the target compound obtained in each of the above reactions can be easily isolated from the reaction mixture by conventional isolation means such as organic solvent extraction, chromatography, recrystallization, distillation, etc. And can be further purified by conventional purification means.
  • the 1-phenylpiperidine derivative represented by the formula (2) includes a 1-phenylpiperidine compound represented by the formula (3) and a thiol compound represented by the formula (4). Is reacted in an inert solvent in the presence or absence of a base.
  • a known solvent is widely used as long as it is an inert solvent for the reaction. can do.
  • solvents include alcohols such as methanol, ethanol, n-propanol, and iso-propanol, aliphatic or alicyclic hydrocarbon solvents such as hexane, cyclohexane, and heptane, benzene, chlorobenzene, toluene, and xylene.
  • Aromatic hydrocarbon solvents such as methylene chloride, 1,2-dichloroethane, chloroform and other halogenated hydrocarbon solvents, diethyl ether, tetrahydrofuran, 1,4-dioxane and other ether solvents, methyl acetate, ethyl acetate, etc.
  • amide solvents such as N, N-dimethylformamide, solvents such as N-methylpyrrolidone, N, N′-dimethylimidazolinone and acetonitrile. These solvents can be used alone or in combination of two or more as required.
  • inorganic bases and organic bases can be used as the base used in the reaction of the compound of the formula (3) and the compound of the formula (4).
  • the inorganic base include alkali metal carbonates such as sodium carbonate, potassium carbonate and sodium bicarbonate, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal hydrogen such as sodium hydride and potassium hydride.
  • the organic base include alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, and amines such as triethylamine and pyridine. These bases may be used alone or in combination of two or more.
  • Such a base can be used in an amount of usually 1 to 100 equivalents, preferably 1 to 2 equivalents, relative to the 1-phenylpiperidine derivative represented by the formula (3).
  • the use ratio of the 1-phenylpiperidine derivative of the formula (3) and the thiol compound represented by the formula (4) can be appropriately selected from a wide range. Is preferably used in an amount of 1 to 5 mol or more, more preferably 1.0 to 2.0 mol.
  • the reaction is preferably performed from room temperature to the boiling point of the solvent used, and more preferably from room temperature to heating under reflux. The reaction is usually completed in about 0.5 to 24 hours.
  • the target product After completion of the reaction, it may be isolated from the reaction system containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary. Moreover, it is also possible to use for the next reaction process, without isolating a target object from a reaction system.
  • Reaction formula 3 [Wherein, X, Y, R, Z, halo 1 and m are as defined above, and M represents chlorine, bromine, iodine, tosylate, mesylate or triflate. ]
  • the 1-phenylpiperidine derivative represented by the formula (2) reacts with the 1-phenylpiperidine derivative represented by the formula (3) and an alkali metal sulfide such as sodium sulfide.
  • an alkali metal sulfide such as sodium sulfide.
  • a thiol derivative represented by the formula (7) by reacting with an alkylating agent of the formula (8) in an inert solvent in the presence or absence of a base. Is done.
  • a known solvent can be widely used as long as it is an inert solvent for the reaction. .
  • Examples of such a solvent include alcohols such as methanol, ethanol, n-propanol and iso-propanol, amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide, tetrahydrofuran, 1,4- Examples include ether solvents such as dioxane, ester solvents such as methyl acetate and ethyl acetate, and solvents such as N-methylpyrrolidone, N, N′-dimethylimidazolinone, dimethyl sulfoxide, and acetonitrile. These solvents can be used alone or in combination of two or more as required.
  • alkali metal sulfide used in the reaction examples include sodium sulfide, sodium sulfide hydrate, sodium hydrogen sulfide, potassium sulfide, lithium sulfide and the like.
  • Such an alkali metal sulfide can be used in an amount of usually 1 to 20 equivalents, preferably 1 to 2 equivalents, relative to the 1-phenylpiperidine derivative represented by the above formula (3).
  • the use ratio of the 1-phenylpiperidine derivative of the formula (3) and the alkali metal sulfide can be appropriately selected from a wide range, but the latter is used in an amount of 1 to 5 mol or more per 1 mol of the former. It is preferable to use 1.0 to 2.0 moles.
  • the reaction is preferably performed from room temperature to the boiling point of the solvent used, and more preferably from room temperature to heating under reflux.
  • the reaction is usually completed in about 0.5 to 24 hours.
  • the target product may be isolated from the reaction system containing the target product by a conventional method, and the target product can be produced by recrystallization, column chromatography, etc. as necessary. It is also possible to subject the product to the next reaction step without isolation.
  • a known solvent is widely used as long as it is an inert solvent for the reaction. can do.
  • solvents include alcohols such as methanol, ethanol, n-propanol and iso-propanol, amide solvents such as N, N-dimethylformamide, ether solvents such as tetrahydrofuran and 1,4-dioxane, Examples include ester solvents such as methyl acetate and ethyl acetate, and solvents such as N-methylpyrrolidone, N, N′-dimethylimidazolinone, dimethyl sulfoxide, and acetonitrile. These solvents can be used alone or in combination of two or more as required.
  • inorganic bases and organic bases can be used as the base used in the reaction of the thiol derivative of the formula (7) and the alkylating agent of the formula (8).
  • the inorganic base include alkali metal carbonates such as sodium carbonate, potassium carbonate and sodium bicarbonate, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and the like.
  • the organic base include amines such as triethylamine and pyridine. These bases may be used alone or in combination of two or more. Such a base can be used in an amount usually 1 to 20 equivalents, preferably 1 to 4 equivalents, relative to the thiol derivative of the formula (7).
  • the use ratio of the thiol derivative of the formula (7) and the alkylating agent of the formula (8) can be appropriately selected from a wide range, but the latter is 1 to 5 mol relative to 1 mol of the former.
  • the above is preferably used, and more preferably 1.0 to 2.0 mol.
  • the reaction is preferably performed from room temperature to the boiling point of the solvent used, and more preferably from room temperature to heating under reflux. The reaction is usually completed in about 0.5 to 24 hours. After completion of the reaction, it may be isolated from the reaction system containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary. Moreover, it is also possible to use for the next reaction process, without isolating a target object from a reaction system.
  • Reaction formula 4 [Wherein, X, Y, R, Z and m are as defined above. ]
  • the 1-phenylpiperidine derivative represented by Formula (7) can be produced by an oxidation reaction of the 1-phenylpiperidine derivative represented by Formula (2).
  • a solvent inert to the reaction can be widely used.
  • solvents include aliphatic or alicyclic hydrocarbon solvents such as hexane, cyclohexane, and heptane, aromatic hydrocarbon solvents such as benzene, chlorobenzene, toluene, and xylene, methylene chloride, and 1,2.
  • -Halogenated hydrocarbon solvents such as dichloroethane and chloroform
  • alcohol solvents such as methanol and ethanol
  • ester solvents such as methyl acetate and ethyl acetate
  • ketone solvents such as acetone and methyl ethyl ketone
  • N, N-dimethylformamide examples thereof include acetic acid such as amide solvents, nitrile solvents such as acetonitrile and propionitrile, aprotic polar solvents such as N-methylpyrrolidone and N, N′-dimethylimidazolinone. These solvents can be used alone or in combination of two or more as required.
  • Examples of the oxidizing agent used in the oxidation reaction of the 1-phenylpiperidine compound represented by the formula (2) include m-chloroperbenzoic acid, sodium periodate, hydrogen peroxide, and tert-butyl hypochlorite. And sodium hypochlorite.
  • Such an oxidizing agent can be used in an amount of usually 1 to 3 equivalents, preferably 1 to 2.5 equivalents, relative to the 1-phenylpiperidine derivative represented by the formula (2).
  • Sodium tungstate dihydrate can be added as a catalyst.
  • Sodium tungstate dihydrate can be used in an amount of usually 0.001 to 0.2 equivalent, preferably 0.001 to 0.1 equivalent, relative to the 1-phenylpiperidine derivative.
  • the reaction can usually be carried out within a range from ⁇ 78 ° C. to the boiling point of the solvent used, and the reaction is preferably carried out at 0 ° C. to room temperature. Although the reaction time varies depending on the reaction temperature and the like and cannot be generally specified, the reaction is usually completed in about 0.5 to 24 hours.
  • the target compound obtained in each of the above reactions can be easily isolated from the reaction mixture by commonly used isolation means such as organic solvent extraction, chromatography, recrystallization, distillation, etc. Further, it can be purified by ordinary purification means.
  • Representative compounds of 1-phenylpiperidine derivatives represented by formula (1) of the present invention are shown in Table 1 below, and representative compounds of 1-phenylpiperidine derivatives represented by formula (3) of the present invention. Are shown in Table 2 below, but the scope of the present invention is not limited to these compounds.
  • the compounds included in the present invention may have optical isomers resulting from the presence of one or two or more asymmetric carbon atoms or asymmetric sulfur atoms. Body, racemate or diastereomer.
  • the physical properties in the table indicate properties and melting points (° C.), “n-” represents normal, “s-” represents secondary, “t-” represents tertiary, and “cy-” represents Cyclo, “i-” represents iso, “Me” represents a methyl group, “Et” represents an ethyl group, “Pr” represents a propyl group, “Bu” represents a butyl group, and “Ph” represents a phenyl group.
  • the compounds of the present invention can be used for the prevention and control of harmful organisms in agriculture, indoors, forests, livestock, hygiene and in various situations. Specific usage scenes, target pests, and usage methods are shown below, but the contents of the present invention are not limited to these.
  • the compound of the present invention represented by the formula (1) is an agricultural crop such as an edible crop (rice, barley, wheat, rye, oats and other wheat, corn, potato, sweet potato, taro, soybeans, red beans, broad beans. , Peas, beans, beans such as peanuts, etc.), vegetables (cabbage, Chinese cabbage, radish, rice bran, broccoli, cauliflower, cruciferous crops such as komatsuna, pumpkins, cucumbers, watermelons, melons, melons, etc.
  • an edible crop rice, barley, wheat, rye, oats and other wheat, corn, potato, sweet potato, taro, soybeans, red beans, broad beans.
  • Peas, beans, beans such as peanuts, etc.
  • vegetables cabbage, Chinese cabbage, radish, rice bran, broccoli, cauliflower, cruciferous crops such as komatsuna, pumpkins, cucumbers, watermelons, melons, melons, etc.
  • Specific pests include the Lepidoptera of Arthropoda, for example, Helicoverpa armigera, Heliothis spp., Agrotis segetum, Autographa nigrisigna , Nettle moth (Trichoplusia ni), Mamestra brassicae, Spodoptera exigua, Spodoptera litura, etc., Plutella xylostella, etc. , Adoxophyes honmai, Archips fuscocupreanus, Chamonaki (Homona magnanima), Caloptilia theivora, Grapholita molesta, etc.
  • Ginmon leafworm Loxia prunifoliella malinella
  • leafberry Lox
  • etia clerkella etc.
  • Phylllocnistis citrella etc.
  • Phyllonorycter ringoniella etc.
  • Acropepiopsis sapporensis etc. (StathmoC 1-6 alkylcarbonyl group (can it be deleted) poda makesssa) etc.
  • Pterinophora gossypiella, etc. Carposina niponensis, etc., Cossus jezoensis, etc., Nemapogon granella, etc. Helia Oleaga (Parasa lepida), Himekuroiraga (Scopelodes contracus), etc. , Cotton moth (Diaphania indica), Shibatatsuga (Parapediasia teterrella), etc. C Department of cabbage butterfly (Pieris rapae crucivora), etc.,
  • Lumpidae (Lampides boeticus), etc., Ascotis selenaria, etc .; neustrium testaceum, etc., Saturnia japonica, etc. cunea), adult larvae such as grapeberry moss (Endopiza viteana), codling moth (Laspeyresia pomonella), larvae and eggs;
  • Coleoptera for example, Anomala cuprea, beetle (Popillia japonica), Oxycetonia jucunda, Anomala geniculata, and the like. , Ancholymaceae (Melanotus fortnumi), etc.
  • Aulacophora femoralis root worm species (Diabrotica spp.), Kiss beetle beetle (Phyllotreta striolata), beetle horn beetle (Cassida nebulosa), radish beetle (Phaedon brassicae), rice beetle moth (Oulema oryzae), pilican beetle Leptinotarsa decemlineata, etc., Rhynchites heros, etc., Cylas Adults, larvae and eggs, such as weevil (Anthonomus gradis grandis) ⁇ , Sphenophrus venatus vestitus, and the like, Epuraea domina;
  • Heteroptera from the order of the Hemiptera for example, Eurydema rugosum, Eysarcoris lewisi, Eysarcoris parvus, Nyra Stink bug (Plautia stali), Halymorpha mista, etc. , Cletus ig punctiger, etc., Leptocorisa chinensis, etc. Etc. Turtle (Apolygus spinolai), red streaks Kasumi turtle (Stenotus rubrovittalus), Trigonotylus caelestialium (Trigonotylus coelestialium), etc., circle stink bug (Megacopta punctatissimum) of beans stink bug family adult, etc., larvae and eggs;
  • Hemioptera Homoptera for example, Platypleura kaempferi, etc., Arboridia apicalis, Empoasca , Nephotettix virescens, etc.
  • Various biotypes of the whitefly Aleurocanthus spiniferus, silver leaf whitefly (Bemisia argentifolii), tobacco whitefly (Bemisia tabaci), etc.
  • Rami Trialeurodes vaporariorum
  • phylloxera Viteus vitifolii of phylloxera family, etc.
  • Thysanoptera e.g., Thripsapala, Thrips tabarip, Thrips sas Yellow thrips (Frankliniella occidentalis), Croton thrips (Heliothrips haemorrhoidalis), etc.
  • Hymenoptera for example, Athalia rosae ruficornis, Arge pagana, etc., Arge mali, etc., Dryocsmus kuriphilus, etc.
  • Barbet bees (Megachile nipponica nipponica), such as the ants of the antaceae (Formica japonica), Giant giant ants (Camponotus kiusiuensis), black-headed ants (Lasius fuliginosus), fire ant (Solenopsis richteri, S. invicta) And eggs;
  • Flies for example, Spodoptera soya Sayatamabaye (Asphondylia yushimai), etc. Drosophila suzukii and other species of the genus Derophila, Liriomyza trifolii, tomato winged lily (Liriomyza sativae), Chromatomyia horticola, Agromyza ory, Agromyza ory Adults, larvae and eggs such as the fly (Delia platura), the onion fly (Delia antiqua);
  • Orthoptera for example, locust locust (Locusta migratoria), grasshopper (Ruspolia lineosa), crickets (Teleogryllus emma), trochals (Truljalia hibinonis) ), Adults such as grasshoppers (Oxya yezoensis), larvae and eggs;
  • Collembola of the Arthropoda elegans for example, adults, larvae and eggs, such as Sminthurus viridis, Onychiurus matsumotoi, etc .;
  • Isopada of the Arthropoda mollusc for example, adults, larvae and eggs such as Armadillidium vulgare
  • arthropod arachnid Acari from the order of the arthropod arachnid, for example, Polyphagotarsonemus latus, Phytonemus pallidus, etc., Penthaleus major, etc., Brevipalpus lewisi), Southern spider mite (Brevipalpus phoenicis), etc. Oligonychus ununguis), yellow spider mite (Bryobia eharai), Miyakeake mite (Eotetranychuschukankitus), clover spider mite (Bryobia praetiosa),
  • Apple mite (Aculus Schlechtendali), Citrus acarid mite (Aculops pelekassi), Ryukyu mandarin mite (Phyllocoptruta citri), Green rust mite (Eriophyes chibaensis), Tulip rust mite (Aceria tulipae), Gram moth (Aculus fockeui), Cosacarus carinatus, etc., adults, larvae and eggs such as Tyrophagus putrescentiae, Robin tick (Rhizoglyphus robini);
  • Tylenchida of the linear animal genus class for example, Ditylenchus destructor of the family Anguinidae, Tylenchorhynchus claytoni etc. of the family Tylencorinx, ), Southern nematode nematode (Pratylenchus coffeae), etc.
  • Nematodes Criconema jaejuense
  • Anguinaceae strawberry nematodes Nothotylenchus acris
  • Aferenchoides strawberry nematodes Aphelecchoides fragarriae
  • Coleoptera Lymeoptera
  • Xiphinema sp. Trichodols Trichodorus sp., Etc .
  • Examples include fungi and bacteria such as Eumycota, Myxomycota, Bacteriomycota, Actinomycota, and the like.
  • diseases to which the compound of the present invention represented by the formula (1) can be applied include rice blast (Pyricularia oryzae), sesame leaf blight (Cochliobolus miyabeanus), and blight (Rhizoctonia solani). ), Brown rot (Pantoea ananatis), brown stripe (Acidovorax avene subsp. Avenae), leaf sheath brown (Pseudomonas fuscovaginae), white leaf blight (Xanthomonas oryzae pv. Oryzae), bacterial blight (Burkholderia plantarii), etc.
  • Wheat powdery mildew (Erysiphe graminis), red mold (Gibberella zeae), red rust (Puccinia striiformis, P.graminis, P. recondita, P. hordei), snow rot (Typhula sp., Micronectriella nivalis) , Naked smut (Ustilago tritici, U. ),
  • Fish spot disease (Pyrenophora ⁇ teres), leprosy disease (Helminthosporium zonatum Ikata), black spot disease (Pseudomonas syringae pv. Japonica), etc .; citrus black spot disease (Diaporthe citri), common scab (Elsinoe fawcetti), fruit rot (fruit rot) Penicillium digitatum, P. italicum), brown rot (Phytophthora citrophthora ,, P.
  • nicotianae nicotianae
  • black scab Physically scab
  • leucotricha spotted leaf disease (Alternaria mali), black spot disease (Venturia inaequalis), black spot disease (Mycospherella pomi), anthracnose (Colletotrichum acutatum), ring rot (Botryosphaeria berengeriana), red star disease (Gymnosporangium yamadae) Disease (Monilinia fructicola), etc .
  • black scab Venturia nashicola, V.
  • Rust Phakopsora ampelopsidis
  • Blacklot's disease Guignardiawellbidwellii
  • downy mildew Plasmopara viticola
  • black rot Monilinia fructigena
  • black scab Cladosporium viticolum
  • gray mold Botrytis cinerea
  • root cancer Agrobacterium vitis etc .
  • Oyster anthracnose Gloeosporiumakikaki), deciduous disease (Cercospora kaki, Mycoshaerella nawae), etc .
  • Urchin anthracnose Coldletotrichum lagenarium
  • powdery mildew Sphaerotheca fuligisis, Oidi
  • Vine blight Didymella bryoniae
  • vine split disease Feusarium oxysporum
  • downy mildew Pseudoperonospora cubensis
  • plague Phytophthora sp.
  • Hairy root disease (Agrobacterium rhizogens), Cancer disease (Streptomyces sp.), Etc .; Watermelon fruit fouling bacterial disease (Acidovorax avenae pv. Citrulli), etc .; Eggplant vegetable bacterial wilt (Ralstonia solanacearum), etc .; Herpes disease (Alternaria solani), leaf mold disease (Cladosporium fulvum), plague disease (Phytophthora infestans), scab disease (Clavibacter michiganense subsp. Michiganense), stem rot (Pseudomonas corrugata), soft rot disease (Pectovorumum.
  • Eggplant brown spot disease (Phomopsis vexans), powdery mildew (Erysiphe cichoracearum), etc .; cruciferous vegetable black spot disease (Alternaria japonica), white spot disease (Cercosporella brassicae) soft rot disease (Pectobacterium carotovorum subsp. Carotovorum), etc. Rot (Pseudomonas syringae pv. Marginalis), black rot (Xanthomonas campestris pv. Campestris), etc .; lettuce rot (Pseudomonas cichorii, Pseudomonas viridiflava), spotted bacterial disease . Xanthomonas campestris pv vitians) green onions of rust (Puccinia allii) and the like;
  • Soybean purpura (Cercospora kikuchii), black scab (Elsinoe glycines), sunspot (Diaporthe phaseolorum var. Sojae), etc .; bean bean anthracnose (Colletotrichum lindemthianum), etc .; , Brown spot disease (Cercospora arachidicola), etc .; pea bean powdery mildew (Erysiphe pisi), etc .; potato summer plague (Alternaria solani), plague (Phytophthora infestans), leaf rot fungus (Rhizoctonia solani), etc .; strawberry udon Mildew (Sphaerotheca humuli), etc .; tea net rot (Exobasidium reticulatum), white scab (Elsinoe leucospila), red burn (Pseudomonas syringae pv.
  • sugar beet blight (Cercospora beticola), seedling blight (Aphanomyces cochliodes), etc .
  • black spot disease (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa), etc .
  • Gray mold disease Botrytis cinerea
  • mycorrhizal disease Sclerotinia sclerotiorum
  • lawn snow rot Pythium iwayamai, Tyohula incarnate, Fusarium nivale, Sclerotinia borealis), powdery mildew Erysiphe graminis
  • Faringling disease Licoperdon perlatum, Lepista subnudo, Marasmius oreades
  • pseudoleaf rot Ceratobasidium spp.
  • Blight Gaemannomyces graminis
  • curvularia leaf blight Curvularia geniculata
  • Pisium disease Pythium periplocum, Pythium vanterpoolii
  • Rust disease Puccinia spp.
  • Dollar spot disease Sclerotinia homoeocarpa
  • the compound of the present invention represented by the formula (1) is active indoors in a building including a general house, and it harms or rots wood and processed products such as wooden furniture, stored food, clothes, books, etc. It can also be used to control arthropods and fungi that damage our lives. As a specific pest,
  • Termites of the Arthropoda class of insects e.g., Coptotermes formosanus, Reticulitermes speratus, and other reticulitermes termites (Reticulitermes hesperus, R. tibialis, R. flavipes, R. lucifugus, R. santonensis, etc.), American termites (Incisitermesorminor), termite family termites (Odontotermes formosanus), termite family Hodotermopsis jzponica, lepidoptera termite larvae (Cryptotermes domestic, larvae) egg;
  • Coleoptera for example, Sweeophilus zeamais, Sitophilus zeamais, etc.
  • Physcomitridae Tribolium castaneum
  • Hirataka kunustomododoki Tribolium confusum
  • scallop slatted beetle Oryzaephilus surinamensis
  • scallop squirrel Cryptolestes pusillus
  • rioderma sera (Stegobium paniceum), etc.
  • Attagenus unicolor japonicus Anthrenus verbasci, Dermestes maculatus, etc., Leopard Gibbium aequinnoctiale, etc. egg
  • Anthrenus verbasci Dermestes maculatus, etc.
  • Lion Gibbium aequinnoctiale etc. egg
  • Lepidoptera for example, Cadra cautella, Ephestia kuehniella, Plodia interpunctella, etc., Sitotroga cerealella, etc., Tinea translucens), adult larvae such as tiger bisselliella, larvae and eggs; Chatteramidae, for example, adults, larvae and eggs such as Lepinotus reticulatus, Liposcelis bostrychophilus, etc .: Cockroach, for example, adults, larvae and eggs such as the cockroach (Blattella germanica), the cockroach (Periplaneta fuliginosa), the cockroach (Periplaneta japonica);
  • Flies for example adults, larvae and eggs such as Drosophila melangogaster, Piophila casei, etc .
  • Mites of arthropod spiders for example adults, larvae and eggs such as Carroglyphus lactis, such as Tyrophagus putrescentiae, Lardoglyphus konoi, etc .
  • Tyromyces palustris, Coriolus versicolor, etc. that are fungal wood-rotting fungi;
  • the compound of the present invention represented by the formula (1) can also be used to control pests that damage or weaken trees in natural forests, artificial forests, and urban green spaces.
  • Specific pests include the Lepidoptera of Arthropoda, for example, Callitearagentargentata, Chauctoidea (Euproctis pseudoconspersa), Orygiawork approximans, Euproctis subflava, Maimai (Lymantria dispar), etc.
  • Coleoptera for example, Anomala rufocuprea, Heptophylla picea, etc., Agrilus spinipennis, etc., Monochamus alterna, Basilepta pallidula, etc., Weevil weevil (Scepticus griseus), Shirahoshizo insidiosus, etc., Weevil weevil (Sipalinus gigas), etc. aceris) and other adults, larvae and eggs, such as the Rhizopertha dominica.
  • Stink bugs for example, Cinara todocola (Aphididae), Adelges japonicus (Adelges japonicus), Asperiotus cryptomeriae, etc. ceriferus) and other adults, larvae and eggs;
  • Bees for example, adults, larvae and eggs, such as the bee family Pachynematus itoi, the bee family Neodiprion sertifer, the bee family Dryocosmus kuriohilus, etc .;
  • flies for example, Tipula aino, etc., Strobilomyia laricicola, etc., Contarinia inouyei, Contarinia matsusintome, adults such as Contarinia matsusintome, etc.
  • Arthropod spider mites for example adults, larvae and eggs such as Oligonichus hondoensis, Oligonichus ununguis;
  • Examples include the linear animal genus Tylenoptera, for example, Bursaphelenchus xylophilus belonging to the family Parasitaferenx.
  • the compound of the present invention represented by the formula (1) is used internally in vertebrates, particularly warm-blooded vertebrates such as cattle, sheep, goats, horses, pigs, poultry, dogs, cats, fish and the like. Alternatively, it can also be used to prevent, treat or control externally parasitic arthropods, nematodes, flukes, tapeworms, and protozoa.
  • the target animal species include rodents such as mice, rats, hamsters and squirrels, carnivores such as ferrets, avian pets such as ducks and pigeons, experimental animals, and the like.
  • rodents such as mice, rats, hamsters and squirrels, carnivores such as ferrets, avian pets such as ducks and pigeons, experimental animals, and the like.
  • Arthropoda insects for example, Abuidae (Tabanusfirufidens), Akaushiabu (Tabanus chrysurus), Housefly family Musca ⁇ bezzii, Musca domestica, Stomoxys calcitrans, etc. Gasterophilus intestinalis, etc., Hypodermaisbovis, etc., Oestrus ovis, etc., Aldrichina grahami, etc.
  • Fleas eg adult fleas (Pulex irritans), adult fleas (Ctenocephalides canis), larvae and eggs; Lice, for example, Haematopinidae suis, Haematopinidae eurysternus, etc., Damalinia bovis, etc.
  • C. elegans such as caterpillars, swine nematodes, porcine pneumoniae, ciliate nematodes, calf intestinal nodules, etc .: roundworms, eg, roundworms, chicken roundworms, etc .; Lepidoptera, for example, Schistosoma japonicum, liver tetsu, deer birch, Insect pulmonary fluke, Japanese hen's egg fluke, etc .; Tapeworms, for example, foliate tapeworms, extended tapeworms, Benedenta tapeworms, square tapeworms, stamens Tapeworms, rotifers, and the like: Root flagellate of Protozoan phytoflagellate, such as Histomonas, Protoflagellate, such as Leishmania, Trypanosoma, etc., Multiflagellate, such as Giardia, Trichomonas, For example, Trichomonas et al .: Ameb
  • the compound of the present invention represented by the formula (1) is for controlling a pest that directly harms or discomforts the human body, or for maintaining a public health state against a pest that transports or mediates a pathogen. Can also be used.
  • Specific pests include Lepidoptera of Arthropoda, for example, Sphrageidus similis, etc., Kunugiaansundans, etc., Paratha ⁇ ⁇ consocia, etc.
  • Adults, larvae and eggs such as Artona martini; Coleoptera, for example, Xanthochroa waterhousei, and the like,
  • Adults, larvae and eggs such as honey beetles (Paederus fuscipes); Larvae and eggs;
  • Flies for example, Armygeres subalbatus, etc., Cucicoides nipponensis, etc., Chironomus yoshimatsui, etc., Simulium nikkoense, etc.
  • Hirosia humilis Musca domestica, etc.
  • Fannia canicularis etc.
  • Phormia regina etc.
  • Srinaph's perf Adults larvae and eggs
  • Fleas for example adults, larvae and eggs, such as the flea (Pulex irritans); Cockroach, for example, adults, larvae and eggs of the cockroach family, such as Blattella germanica, cockroach (Periplaneta americana), black cockroach (Periplaneta fuliginosa), cockroach (Periplaneta japonica); For example, adults, larvae and eggs such as Diestrammena japonica and Diestrammena apicalis; lice, for example, Pediculus humanus humanus, Pepius pub Adults, larvae and eggs, etc .; stink bugs, for example, adults, larvae and eggs of the genus Isyndus obscurus, such as Cimex lectularius;
  • Collembola for example, adults, larvae and eggs, such as Hypogastrura communis from the order of the Arthropoda elegans; Ticks (Ixodes persulcatus), etc., mite (Ornithonyssus bacoti), etc.
  • Adults, larvae and eggs such as Dermotophagoides pteronyssinus, Scaroptes scabiei, etc., Trombicula akamushi, etc .;
  • Genuine spiders for example, Chiracanthium japonicum, etc., Heteropoda venatoria, etc., Spermophora senoculata, Pholcus ), Etc., adults, larvae and eggs such as Plexippus paykulli, Plexippus adansoni; adults, larvae and eggs such as scorpions, for example, Isometrus europaeus; Arthropods of the Coleoptera, Lipids, for example, adults, larvae and eggs such as Scolopendra subspinipes mutilans, Scolopendra subspinipes japonica; Adult larvae, etc. Fine egg; Obiyasude eyes of Arthropoda Diplopoda, for example, of Yakeyasude family Yakeyasude (Oxidus gracilis) adults such as, larvae and eggs;
  • Isopods of arthropod crustaceans for example adults, larvae and eggs, such as Porcellio cabscaber; Annelids of annelida, for example, Haemadipsa zeylanica japonica Trichophyton rubrum, Trichophyton mentagrophytes, etc. which are tinea fungi, Candida albicans, etc., Candida fungi, fungi such as Aspergillus fumigatus, Gram-negative bacteria such as Escherichia coli Escherichia coli, Pseudomonas aeruginosa, etc. Gram-positive bacteria such as Staphylococcus ocaureus are included.
  • the compound of the present invention represented by the formula (1) is a pest that damages crops, natural forests, artificial forests, trees in urban green spaces and ornamental plants, such as arthropods, gastropods, nematodes. It is particularly valuable for controlling fungi and fungi.
  • the compounds of the present invention may be used in other commercially active formulations, such as insecticides, acaricides, nematicides, in their commercially useful formulations and use forms prepared by these formulations. It can also be present as a mixture with fungicides, synergists, plant regulators, baits or herbicides.
  • Use forms include wettable powders, granular wettable powders, dry flowable powders, aqueous solvents, emulsions, liquids, oils, flowables such as suspensions in water and emulsions in water, capsules, powders, granules, Fine granules, baits, tablets, sprays, fumes, aerosols and the like can be taken.
  • various agricultural chemical adjuvants conventionally used in the technical field of agricultural and horticultural medicine can be appropriately used.
  • Such agrochemical adjuvants can be used for the purpose of, for example, improving the effects, stabilizing, and improving dispersibility of agricultural and horticultural chemicals.
  • Examples of the agricultural chemical adjuvant include a carrier (diluent), a spreading agent, an emulsifier, a wetting agent, a dispersing agent, a disintegrating agent, and the like.
  • Liquid carriers include water, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, butanol and glycol, ketones such as acetone, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, methyl Mention may be made of naphthalene, cyclohexane, animal and vegetable oils, fatty acids and the like.
  • clay kaolin, talc, diatomaceous earth, silica, calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina, sawdust, nitrocellulose, starch, gum arabic and the like can be used.
  • a normal surfactant can be used as the emulsifier and the dispersant.
  • anionic surfactants such as higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, lauryl betaine, etc.
  • Cationic surfactants, nonionic surfactants, amphoteric surfactants, and the like can be used.
  • spreading agents wetting agents such as dialkyl sulfosuccinate; fixing agents such as carboxymethyl cellulose and polyvinyl alcohol; disintegrating agents such as sodium lignin sulfonate and sodium lauryl sulfate can be used.
  • the compound of this invention can also be mix
  • the content of the compound of the present invention as an active ingredient is, for example, 0.01 to 99.5% by mass, preferably selected from the range of 0.5 to 90% by mass.
  • an emulsion it can be produced so as to contain an active ingredient of about 1 to 90% by weight, preferably 10 to 40% by weight.
  • plant stems and leaves are usually used in places where damage is caused by these pests or where damage may occur.
  • all soil layers are mixed, applied to the soil, mixed with floor soil, treated with cell seedlings, treated with planting holes, treated with plant roots, treated with top dresses, boxed rice, applied to water, etc. It can also be absorbed from the roots. It can also be used by soaking seeds in chemicals, seed dressing, seed treatment such as calper treatment, application to nutrient solution in nutrient solution (hydroponic) cultivation, smoke, or trunk injection.
  • seed dressing seed treatment
  • seed treatment such as calper treatment
  • application to nutrient solution in nutrient solution (hydroponic) cultivation smoke, or trunk injection.
  • it varies depending on the type and amount of pests, the type of target crop / tree, cultivation form, and growth state, but generally 0.1 to 1000 g, preferably 1 to 100 g per 10 are. Apply.
  • the method of applying to plant stock or seedling nursery, etc., the method of spraying granules to the plant stock or seedling nursery, etc., powder, wettable powder, granulated water before sowing or transplanting A method of spraying Japanese powder, granule, etc. and mixing with the whole soil, before sowing or planting plant, powder, wettable powder, granule wettable powder, granule, fine granule, etc. The method of spraying etc. is mentioned.
  • wettable powders For wettable powders, granular wettable powders, aqueous solvents, emulsions, liquids, flowables such as suspensions in water and emulsions in water, capsules, etc., dilute with water and generally apply 5 to 500 liters per 10 ares.
  • powder, granule, fine granule or bait, etc. it should be evenly applied to the whole area to be treated. What is necessary is just to spread on the soil surface. Spraying or irrigation may be done around seeds, crops or trees that you want to protect from harm. Further, the active ingredient can be mechanically dispersed by tilling during or after spraying.
  • the dosage form may differ depending on the time of application such as application at seeding, greening period, application at transplanting, etc., for example, powder, granule wettable powder, granule, fine powder What is necessary is just to apply in dosage forms, such as a granule. It can also be applied by mixing with soil, and it can be mixed with soil and powder, granulated wettable powder, granule or fine granule, etc. it can. Alternatively, the culture medium and various preparations may be applied alternately in layers.
  • solid preparations such as jumbo agents, packs, granules, granule wettable powders, and liquid preparations such as flowables and emulsions are usually sprayed on flooded paddy fields.
  • an appropriate preparation can be sprayed and injected into the soil as it is or mixed with fertilizer.
  • a chemical solution such as emulsion or flowable as a source of water flowing into a paddy field such as a water mouth or an irrigation device, it can be applied in a labor-saving manner along with the supply of water.
  • Seed treatment methods include, for example, a method in which a liquid or solid preparation is diluted or undiluted to immerse the seed in a liquid state to attach and permeate the drug, and a solid preparation or liquid preparation is mixed with the seed.
  • a method of dressing and adhering to the surface of the seed examples thereof include a method of dressing and adhering to the surface of the seed, a method of coating the seed by mixing with an adhesive carrier such as a resin and a polymer, and a method of spraying around the seed simultaneously with planting.
  • the “seed” for performing the seed treatment means a plant body at an early stage of cultivation used for plant propagation, for example, a seed, a bulb, a tuber, a seed bud, a stock bud, a basket, a bulb or a nutrient for cultivation of cuttings.
  • the “soil” or “cultivation carrier” of a plant in the case of application refers to a support for cultivating crops, particularly a support for growing roots, and the material is not particularly limited. Any material can be used as long as it can grow, so-called soil, seedling mat, water, etc. Specific examples of materials include sand, pumice, vermiculite, diatomaceous earth, agar, gel-like substances, polymer substances, Examples thereof include rock wool, glass wool, wood chips, and bark.
  • the irrigation treatment of the liquid drug or the granule spraying treatment to the seedling nursery is preferred.
  • the compound of the present invention represented by the formula (1) protects wood (standing trees, fallen trees, processed woods, storage woods or structural woods) from harms of insects such as termites or cucumbers and fungi. Is also worthy. In such a situation, control with oil, emulsion, wettable powder, sol spray, injection, irrigation, application, powder, granule spray, etc. on wood or surrounding soil. Can do. In addition, oils, emulsions, wettable powders, powders, etc. used in this scene are used with other active compounds such as insecticides, acaricides, nematicides, fungicides, repellents or synergists.
  • the total amount of the active ingredient compounds is 0.0001 to 95% by mass, preferably 0.005 to 10% by mass for oils, powders and granules, emulsions and wettable powders, and the like.
  • the sol may contain 0.01 to 50% by mass.
  • When controlling arthropods or fungi apply 0.01 to 100 g of active ingredient compound per 1 m 2 to the soil or wood surface.
  • the compound of the present invention represented by the above formula (1) is used for storing cereals, fruits, nuts, spices, tobacco and other products as they are, in a powdered state, or mixed in the product. In addition, it can be used to protect against damages such as Lepidoptera, Coleoptera, Mites and Fungi.
  • animal products skin, hair, wool, feathers, etc.
  • plant products cotton, paper, etc.
  • Lepidoptera, Coleoptera, Spots and Cockroaches It can be protected, and can be protected from attacks by Lepidoptera, Coleoptera, flies and ticks when storing food such as meat and fish.
  • methods such as spraying oils, emulsions, wettable powders, powders, etc., setting up resin transpiration agents, treating smoke and fumes, setting up granules, tablets and poison baits, spraying aerosols, etc. Can be controlled with.
  • formulations can also be present as a mixture with other active compounds such as insecticides, acaricides, nematicides, fungicides, repellents or synergists, in these formulations. May contain 0.0001 to 95% by mass of the total amount of active ingredient compounds.
  • the compound of the present invention represented by the above formula (1) is a disease of arthropods and fungi, humans and livestock that parasitize the body surface of humans and livestock and cause direct harm such as eating or sucking blood on the skin. Valuable in combating or preventing arthropods, nematodes, flukes, tapeworms, protozoa, and arthropods that cause discomfort to humans There is.
  • the compound of the present invention is mixed into a small meal or feed, or a suitable pharmaceutical composition that can be taken orally, such as a tablet or pill containing a pharmaceutically acceptable carrier or coating substance.
  • a suitable pharmaceutical composition that can be taken orally, such as a tablet or pill containing a pharmaceutically acceptable carrier or coating substance.
  • a pharmaceutically acceptable carrier or coating substance such as a pharmaceutically acceptable carrier or coating substance.
  • the active ingredient compound is generally contained in the preparation in an amount of 0.0001 to 0.1% by mass, preferably 0.001 to 0.01% by mass.
  • a device for example, a collar, a medallion, an ear tag, or the like
  • a device for example, a collar, a medallion, an ear tag, or the like
  • an animal so as to control an arthropod locally or systemically can be used.
  • beverage When administered orally as medicinal drinking water, the beverage is usually dissolved, suspended or dispersed in a suitable non-toxic solvent or water with a suspending or wetting agent such as bentonite or other excipients. is there.
  • a suspending or wetting agent such as bentonite or other excipients.
  • beverages also contain an antifoam agent.
  • Beverage formulations generally contain 0.01 to 1.0% by weight, preferably 0.01 to 0.1% by weight, of the active ingredient compound.
  • capsules, pills or tablets containing a predetermined amount of the active ingredient are usually used.
  • These forms of use should be homogeneously mixed with a suitably pulverized diluent, filler, disintegrant and / or binder such as starch, lactose, talc, magnesium stearate, vegetable gum, etc. Manufactured by.
  • a suitably pulverized diluent, filler, disintegrant and / or binder such as starch, lactose, talc, magnesium stearate, vegetable gum, etc.
  • Such unit use formulations can vary widely in the anthelmintic mass and content depending on the type of host animal to be treated, the degree of infection and the type of parasite and the body weight of the host.
  • the active ingredient compound When administered by animal feed, it can be dispersed homogeneously in the feed, used as a top dressing or in the form of pellets.
  • the active ingredient compound is contained in the final feed in an amount of 0.0001 to 0.05% by mass, preferably 0.0005 to 0.01% by mass.
  • a liquid carrier vehicle can be administered parenterally to animals by intragastric, intramuscular, intratracheal or subcutaneous injection.
  • the active compounds are preferably mixed with suitable vegetable oils, such as peanut oil, cottonseed oil.
  • suitable vegetable oils such as peanut oil, cottonseed oil.
  • Such a formulation generally contains 0.05 to 50% by mass, preferably 0.1 to 5.0% by mass of the active ingredient compound.
  • It can also be administered topically by mixing with a suitable carrier such as dimethyl sulfoxide or a hydrocarbon solvent. This formulation is applied directly to the external surface of the animal by spraying or direct injection.
  • the compound of the present invention represented by the above formula (1) has potential to be a pest as an anthelmintic agent for arthropods that cause direct harm or arthropods that are disease vectors.
  • the preparations in these usage forms may exist as a mixture with other active compounds, for example, pest control agents, mite control agents, nematode control agents, disease control agents, repellents or synergists.
  • the active ingredient compound is contained in a total amount of 0.0001 to 95% by mass.
  • the compound of the present invention represented by the formula (1) can be present as a mixture with other active compounds.
  • pests such as arthropods, gastropods and nematodes that cause damage to plants by mixing with compounds (insecticides) having pest control activity, tick control activity or nematode control activity
  • pests to be controlled can be expanded, and a synergistic effect such as a reduction in dosage can be expected.
  • Illustrative active compounds include organophosphorus agents such as acephate, azinphos-methyl, chlorpyrifos, diazinon, dichlorvos, dimeton-S-methyl.
  • Carbamates such as alanycarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbofuran, carbosulfan, ethiofencarb, fenobucarb, furothiocarb (Furathiocarb), isoprocarb, mesomyl, metolcarb, pirimicarb, propoxur, thiodicarb, etc .; organic chlorinating agents such as aldrin, chlordane , DDT (p, p'-DDT), endosulfan, lindane, etc .; pyrethroids such as acrinathrin, allethrin, bifenthrin, cycloprothrin Cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, deltamethrin, ethofenprox, fenpropathrin, fenvalerate, fluc
  • Neonicotinoid agents such as acetamiprid, clothianidin, dinotefran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, thiamethoxam, etc .; Chlorantraniliprore, cyantraniliprore, cyclaniliprore, flubenziamid, etc .; phenylpyrazoles such as ethiprole, fipronil, acetoprole ), Pyrafluoprole, pyriplore, etc .; nereistoxin agents such as bensultap, cartap, thiocyclam, thiosult ap) etc .; insect growth regulators such as phenylbenzoylurea and diacylhydrazines, such as chlorfluazuron, diflubenzuron, flufenoxuron, hexaflumuron, lufenuron ( lufen
  • Juvenile hormone agents such as diofenolan, phenoxycarb, hydroprene, metoprene, pyriproxyfen, etc .
  • insecticidal substances produced by microorganisms such as abamectin ( abamectin), emamectin-benzoate, ivermectin, ivermectin, lepimectin, milbemectin, nemadectin, nikkomycin, polyoxin, spinetoram, spinodram (Spinosad), BT agents, etc .
  • insecticides derived from natural products such as anabasine, azadiractin, deguelin, fatty acid glycerides (decanolyoctanoylglycerol), hydroxypropyl starch (hydroxy propy) l starch), soy lecithin, nicotine, nornicotine, sodium oleate (oreic acid sodium salt), machine oil (
  • insecticides include, for example, afidpyropen, chlorfenapyr, diafenthiuron, DBEDC (Dodecylbenzenesulphonic acidbisethylenediamine copper [II] salt), flonicamid, flumetoliquine, flumetoquin ), Flupradidifurone, hydramethylnon, indoxacarb, metaflumizone, metaldehyde, nicotinsulfate, pymetrozine, pyridalyl, pyriflutazone (Pyrifluquinqzon), spirotetramat, sulfoxaflor, tolfenpyrad, triazamate, etc .;
  • Acaricides such as acequinocyl, amidoflumet, amitraz, azocyclotin, benzoximate, bifenazate, binapacryl, phenisobromolate, bromopropylate, Chinomethionat, clofentezine, cyenopyrafen, cyflumetofen, tricyclohexyltin hydroxide, dichexol, dienochlor, etoxazole, fenazaflor , Fenazaquin, fenbutatin oxide, fenothiocarb, fenpyroximate, fluacrypyrim, hexytazox (hexyt) hiazox), pyrimidifen, polynactins, propargite, pyflubumide, pyridaben, spirodiclofen, spiromesifen, tebufenpyrad, tebufenpyrad,
  • Nematicides such as aluminum phosphide, benclothiaz, cadusafos, ethoprophos, fluensulfone, fosthiazate, furfural, imimiafos Levamisol hydrochloride, mesulfenfos, metam-ammonium, methyl isothiocyanate, moranteltartarate, oxamyl, thioxazafen, etc .; Examples include chlorphacinone, coumatetralyl, diphacinone, sodium fluoracetate, warfarin and the like.
  • the compound of the present invention represented by the above formula (1) can also be present as a mixture with other active compounds other than compounds having pest control activity, mite control activity and nematode control activity.
  • other active compounds other than compounds having pest control activity, mite control activity and nematode control activity.
  • the control effort is reduced and the dosage is reduced.
  • a synergistic effect can be expected.
  • more effective control effects, such as a synergistic effect can be expected by using a mixture with a repellent or a synergist.
  • Specific active compounds thereof include disease control agents such as DD (1,3-dichloropropene), acibenzolar-S-methyl, aldimorph, ametoctradin, amisulbrom, and Prim (andoprim), triazine (anilazine), azaconazole (azaconazole), azoxystrobin (basic copper sulfate), benodanil (benodanil), benomyl (bennomyl), benthiavalicarb (benthiavalicarb) -isopropyl), benhiazole, bitertanol, bixafen, blasticidin S, boscalid B, bromuconazole, calcium carbonate, butiobate buthiobate), lime-sulfur mixture sulfide, captafol, captan, carbendazim, carboxin, carpropamid, chinomethionat, chlorfenazole, chloroneb chloropicrin
  • Compounds having herbicidal activity include, for example, aclonifen, acifluofe n-sodium, alachlor, alloxydim, amicarbazone, amidosulfuron, anilofos , Asuram, atrazine, azimsulfuron, benfuresate, bensulfuron-methyl, bentazone, benthiocarb, benzobicyclon, benzofe Benzofenap, bialaphos, bifenox, bromobutide, bromoxynil, butamifos, cafenstrole, calcium peroxide, carbeta Carbetamide, cinosulfuron, clomeprop, cyclosulfamuron, cyhalofop-butyl, daimuron, desmedipham, diclofopop -methyl), diflufenican, dimefuron, dimethametryn, dinoterb, diquat,
  • Examples of compounds having a plant growth regulating action include 1-naphthylacetic acid (1-naphthylacetic acid), 4-CPA (4-CPA), benzylaminopurine, 6-benzylaminopurine, butralin, calcium chloride ( calcium chloride, calcium formate (calcium peroxide), calcium sulfate (calcium sulfate), chlormequat chloride, choline, cyanamide, cyclanilide, daminozide ), Decyl alcohol, dichlorjoprop, ethephon, etychlozate, flurprimidol, forclorfenuron, gibberellic acid, indolebutyric acid (Indolebutyric acid), maleic acid Radium potassium (maleic hydrazide potassium salt), mefenpyr, mepiquat chloride, oxine ⁇ sulfate, 8-hydroxyquinoline sulfate, paclobutrazol, paraffin, prohexa
  • Repellents such as capsaicin, carane-3,4-diol, citronellal, deet, dimethyl phthalate, hinokitiol, limonene ), Linalool, menthol, menthone, naphthalene, thiram, etc .;
  • Synergists such as methylenedioxynaphthalene, naphthyl propynyl ether, nitrobenzyl thiocyanate, octachlorodipropyl ether, pentynyl phthalimide), phenyl salioxon, piperonyl butoxide, safrole, sesamex, sesamin, sulfoxide, triphenyl phosphate, verbutin Etc.
  • the compound of the present invention is used as a biopesticide, for example, cytoplasmic polyhedrosis virus (CV), insect pox virus (Entomopox virus, EPV), granulosis virus (Granulosis virus, GV), nuclear polyhedrosis virus (Nuclear). virus preparations such as polyhedrosisVvirus ⁇ (NPV), Beauveria bassiana, Beauveria brongniartii, Monocrosporium phymatophagum, Paeciloosepas , Steinernema carpocapsae, Steinernema glaseri, Steinernema kushidai, Verticillium lecanii, etc.
  • CV cytoplasmic polyhedrosis virus
  • EPV insect pox virus
  • Gnulosis virus granulosis virus
  • Nuclear nuclear polyhedrosis virus
  • virus preparations such as polyhedrosisVvirus ⁇ (NPV), Beauveria bass
  • Microbial pesticides utilized as insecticides or nematicidal agents Agrobacterium Liu um radiobacter (Agrobacterium radiobactor), Bacillus subtilis (Bacillus subtilis), nonpathogenic Erwinia carotovora (Erwinia carotovora,
  • biopesticides for example, Amblyseius californicus, Amblyseius cucumeris, Amblyseius degenerans, Aphidius colemani, Aphidoletes aphid, (Chrysoperia carnea), honey bee (Dacnusa sibirica), Isaea eel wasp (Diglyphus isaea), Onsatsu wasp (Encarsia formosa), Sabakutsue bee (Eretmocerus eremicus), Arigata lin othia oth , Hemiptarsenus varicornis, Hyochgrimidhi hornet (Neochrysocharis formosa), Orius sauteri, Orius strigicollis, Phyto red mite (Phyto) natural enemies such as seiulus ⁇ ⁇ persimilis, black leopard turtle (Pilophorus ⁇ ⁇ typic
  • Example 1-1 Synthesis of 2,5-difluoro-4- [4- (trifluoromethyl) piperidin-1-yl] benzonitrile (Compound No. B-1): 4-Trifluoromethylpiperidine (1.68 g) and potassium carbonate (1.65 g) were added to a solution of 2,4,5-trifluorobenzonitrile (1.57 g) in N, N-dimethylformamide (25 ml). The reaction mixture was stirred at room temperature for 15 minutes, water (50 ml) and ethyl acetate (50 ml) were added, the organic layer was separated, and the organic layer was further washed with water.
  • Compound No. B-1 4-Trifluoromethylpiperidine (1.68 g) and potassium carbonate (1.65 g) were added to a solution of 2,4,5-trifluorobenzonitrile (1.57 g) in N, N-dimethylformamide (25 ml). The reaction mixture was stirred at room temperature for 15 minutes
  • the reaction mixture was cooled to room temperature, water (50 ml) and ethyl acetate (30 ml) were added, the organic layer was separated, and the organic layer was further washed with water. After drying the organic layer with MgSO 4 , the organic solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain 0.38 g (mp76-78 ° C.) of 5-fluoro-2-propylthio-4- [4- (trifluoromethyl) piperidin-1-yl] benzonitrile.
  • Example 2 2-1 Synthesis of 2,5-difluoro-4- [4- (trifluoromethyl) piperidin-1-yl] benzaldehyde (Compound No .: B-2):
  • the reaction solution was poured into saturated aqueous sodium hydrogen carbonate and the organic layer was extracted. The obtained organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The desiccant was filtered off and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography, and 1-fluoro-3-methyl-4- (2,2,2-trifluoroethylsulfinyl) -6- [4- (trifluoromethyl) piperidin-1-yl] benzene Of 0.16 g (mp116-118 ° C.).
  • Example 3.3-1 Synthesis of 2- (cyclopropylmethylthio) -5-fluoro-4- [4- (trifluoromethyl) piperidin-1-yl] benzonitrile (Compound No .: A-19): 2,5-difluoro-4- (4- (trifluoromethyl) piperidin-1-yl) benzonitrile (B-1) (1.16 g) was dissolved in DMF (20 ml) and sodium hydrosulfide n hydrate was added. (0.45 g) was added, and the mixture was stirred at 80 ° C. for 3 hr. After cooling to 70 ° C.
  • cyclopropylmethyl iodide (0.87 g) and potassium carbonate (0.77 g) were added, and the mixture was stirred for 15 min, heated to 80 ° C., and stirred for 4 hr. After allowing to cool, it was released into water (100 ml), extracted with ethyl acetate (50 ml), and the organic layer was washed 5 times with brine (50 ml).
  • Chloroform 3-1 were synthesized 2- (cyclopropylmethyl) -5-fluoro-4- [4- (trifluoromethyl) piperidin-1-yl] benzonitrile (A-19) (0.36 g) (5 ml ), 70% m-chloroperbenzoic acid (0.24 g) was added at room temperature, and the reaction was stirred at room temperature overnight.
  • a sodium carbonate aqueous solution (10 ml) and chloroform (5 ml) were added to separate the organic layer, and the organic layer was further washed with water. After drying the organic layer with MgSO 4 , the organic solvent was distilled off under reduced pressure.
  • Example 4 Synthesis of 1-fluoro-3-methyl-4- (2,2,2-trifluoroethylsulfinyl) -6- [4- (trifluoromethyl) piperidin-1-yl] benzene (Compound No .: A-28) : 1-Fluoro-3-methyl-4- (2,2,2-trifluoroethylthio) -6- [4- (trifluoromethyl) piperidin-1-yl] benzene (A-27) synthesized in Example 2 : 35% -hydrogen peroxide solution (4.75 g) and sodium tungstate dihydrate (5 mol%) were added to a solution of 18.3 g) in methanol (140 mL) at room temperature and stirred at the same temperature for 6 hr.
  • Example 6 1-fluoro-3-methoxymethyl-4- (2,2,2-trifluoroethylsulfinyl) -6- [4- (trifluoromethyl) piperidin-1-yl] benzene (Compound No .: A-85) Synthesis: In the same manner as in Example 4, 1-fluoro-3-methoxymethyl-4- (2,2,2-trifluoroethylthio) -6- [4- (trifluoromethyl) piperidin-1-yl] benzene ( Compound No .: A-84) to 1-fluoro-3-methoxymethyl-4- (2,2,2-trifluoroethylsulfinyl) -6- [4- (trifluoromethyl) piperidin-1-yl] benzene ( mp 134-136 ° C) was obtained in 84% yield.
  • Table 1 shows the 1 H-NMR data of compounds produced in the same manner as in the above Examples.
  • Table 3 shows the 1 H-NMR data of compounds produced in the same manner as in the above Examples.
  • Formulation Example 1 Emulsion Compound of the present invention (10 parts), xylene (60 parts), N-methyl-2-pyrrolidone (20 parts), Solpol 3005X (mixture of nonionic surfactant and anionic surfactant, Toho Chemical Industry Co., Ltd. (trade name) (10 parts) was uniformly mixed and dissolved to obtain an emulsion.
  • Formulation Example 2 Wetting Agent-1 Compound of the present invention (20 parts), Nipseal NS-K (white carbon, Tosoh Silica Co., Ltd., trade name) (10 parts), Kaolin clay (Kaolinite, Takehara Chemical Co., Ltd., trade name) (60 parts) Sun extract P-252 (sodium lignin sulfonate, Nippon Paper Chemical Co., Ltd., trade name) (5 parts) and Lunox P-65L (alkyl allyl sulfonate, Toho Chemical Industry Co., Ltd., trade name) (5 parts) was uniformly mixed and ground with an air mill to obtain a wettable powder.
  • Nipseal NS-K white carbon, Tosoh Silica Co., Ltd., trade name
  • Kaolin clay Kaolin clay
  • Sun extract P-252 sodium lignin sulfonate, Nippon Paper Chemical Co., Ltd., trade name
  • Lunox P-65L alkyl allyl sulfonate,
  • Formulation Example 4 Aqueous solvent-1 Compound (20 parts) of the present invention, Lunox P-65L (alkyl allyl sulfonate, Toho Chemical Industry Co., Ltd., trade name) (3 parts), water-soluble carrier (potassium chloride) (77 parts) are uniformly mixed and pulverized Thus, an aqueous solvent was obtained.
  • Lunox P-65L alkyl allyl sulfonate, Toho Chemical Industry Co., Ltd., trade name
  • water-soluble carrier potassium chloride
  • Formulation Example 5 Aqueous solvent-2 Uniformly mix the compound of the present invention (50 parts), Newkalgen BX-C (Na alkylnaphthalene sulfonate, Takemoto Yushi, trade name) (5 parts), silicon dioxide (2 parts), water-soluble carrier (43 parts) The mixture was pulverized to obtain an aqueous solvent.
  • Newkalgen BX-C Na alkylnaphthalene sulfonate, Takemoto Yushi, trade name
  • silicon dioxide 2 parts
  • water-soluble carrier 43 parts
  • Formulation Example 8 EW-1 Mixing and homogenizing the compound of the present invention (20 parts) with Solpol CA-42 (nonionic activator, Toho Chemical Co., Ltd., trade name) (15 parts) and preservative Proxel GX-L (0.1 parts) After stirring, water (59.6 parts) was gradually added with stirring to obtain a dispersion.
  • Antifoam anti-home E-20 emulsion type modified silicone, Kao Corporation, trade name
  • xanthan gum dispersed in propylene glycol 5.0 parts
  • 0.2 parts was added to obtain an emulsion formulation (phase inversion emulsification method).
  • Formulation Example 12 ME Agent-3
  • solvent Solvesso 200 (0.08 part)
  • Neukalgen ST-30 polyoxyethylene arylphenyl ether formaldehyde condensate, polyoxyalkylene arylphenyl ether, alkylbenzene sulfonate, and xylene.
  • Takemoto Oil & Fat Co., Ltd., trade name (0.12 parts)
  • surfactant 0.1 part
  • water 99.69 parts
  • Formulation Example 13 Granules-1
  • the compound of the present invention (5 parts), bentonite (30 parts), clay (60 parts), sodium lignin sulfonate (5 parts) were uniformly pulverized and mixed, mixed well with water, extruded and granulated, Granules were obtained by dry sizing.
  • Formulation Example 14 Granules-2 Silica sand (90 parts) was put in a rolling granulator, and after adding water, the compound of the present invention (5 parts), sodium lignin sulfonate (4 parts), polyvinyl alcohol (PVA) that had been pulverized and mixed in advance. (0.5 part) and white carbon (0.5 part) were added and coated, and then dried and sized to obtain granules.
  • the compound of the present invention 5 parts
  • sodium lignin sulfonate 4 parts
  • PVA polyvinyl alcohol
  • white carbon 0.5 part
  • Formulation Example 15 Granules-3 Ishikawa Lite (89 parts) was put into a rolling granulator, and after adding water, the compound of the present invention (5 parts), sodium lignin sulfonate (3 parts), dioctyl sulfosuccinate that had been pulverized and mixed in advance. Sodium (0.5 part), POE styryl phenyl ether (2 parts) and polyvinyl alcohol (PVA) (0.5 part) were added, coated, and then dried to obtain granules.
  • PVA polyvinyl alcohol
  • Fine granules-1 The compound of the present invention (2 parts) was diluted with a solvent, and mixed with pumice (98 parts) as an extender while spraying the diluent. The obtained granular composition was dried and sieved to obtain a fine granule.
  • Fine Granule-2 The compound of the present invention (5 parts) was subjected to air mill grinding or mechanochemical grinding as required.
  • the powdery raw material and silica sand (85 parts) as an extender are uniformly mixed, and then mixed with sprayed binder Toxanone GR-31A (10 parts) diluted with a solvent, and the resulting granular composition After drying, it was sieved to obtain a fine granule.
  • Formulation Example 18 Powder A compound (5 parts) of the present invention was uniformly mixed with white carbon (5 parts) and clay (trade name, Nippon Talc Co., Ltd.) (90 parts) and pulverized to obtain a powder.
  • Formulation Example 19 DL Powder A propylene glycol (0.5 part) and DL clay (94.5 parts) were uniformly mixed with the compound of the present invention (5 parts) and pulverized to obtain a powder.
  • Formulation Example 20 Seed Coating Powder A compound of the present invention (10 parts), sodium lignin sulfonate (6 parts), polyvinyl alcohol (PVA) (1 part) and clay (trade name, Nippon Talc Co., Ltd.) (83 parts) The powder prepared by mixing and pulverizing was mixed with pre-moistened seeds and air-dried to obtain coated seeds.
  • PVA polyvinyl alcohol
  • clay trade name, Nippon Talc Co., Ltd.
  • the compound used for the comparison control is a compound represented by the following formula.
  • Comparative agent A 22-11 described in WO 2006/087162
  • Test Example 1 Density suppression test against a spider mite A 430 ml polyethylene cup filled with water was capped with a hole (diameter: about 5 mm) in the center. Absorbent cotton having a width of about 1 cm and a length of about 14 cm was inserted so as to be immersed in the water in the cup through the hole of the lid, and about 8.0 cm square of absorbent cotton was placed on the absorbent cotton. In this way, two leaf discs (diameter 2 cm) made from kidney bean primary leaves are placed on the absorbent cotton that is constantly replenished with water in the cup so that the back of the leaf is on top. Inoculated with 5 adult female nymph mite.
  • This cup was placed in an acrylic cylinder having a height of 45 cm and a diameter of 12 cm, and an aqueous dilution of an emulsion (500 ppm) prepared according to Formulation Example 1 was sprayed using an air brush (1 concentration). 1 iteration). After spraying, it was kept in a constant temperature room at 25 ° C.
  • Next-generation density suppression effect on eggs laid by adults 7 days after treatment 100 (density suppression rate: 100%), 95 (same: 99-95%), 80 (same: 94-80%), 50 (same: 79-50%) and 0 (same: less than 50%), and the next generation density suppression rate was calculated using the following formula based on the results.
  • Next-generation density suppression rate (A x 100 + B x 95 + C x 80 + D x 50) / (A + B + C + D + E)
  • A 100 disks
  • B 95 disks
  • C 80 disks
  • D 50 disks
  • E 0 disks
  • Test Example 2 An insecticidal test against citrus red mite A 430 ml polyethylene cup filled with water was capped with a hole (diameter: about 5 mm) in the center. Absorbent cotton having a width of about 1 cm and a length of about 14 cm was inserted so as to be immersed in the water in the cup through the hole of the lid, and about 8.0 cm square of absorbent cotton was placed on the absorbent cotton. In this way, two leaf discs (diameter 2 cm) made from citrus fully expanded leaves are placed on the absorbent cotton that is constantly replenished with water in the cup, and six mandarin mite female adults are placed on the leaf discs. Vaccinated.
  • This cup was placed in an acrylic cylinder having a height of 45 cm and a diameter of 12 cm, and an aqueous dilution of an emulsion (500 ppm) prepared according to Formulation Example 1 was sprayed using an air brush (1 concentration). 1 iteration). After spraying, it was kept in a constant temperature room at 25 ° C.
  • Four days after the treatment the life and death of adult worms and bitter melon were investigated under the binocular, and the mite killing rate (%) [(number of dead mites / number of tested ticks) ⁇ 100] was determined by dying the bitter worms.
  • the comparative agent A had a miticide rate of 0%.
  • Test example 3 Soil irrigation treatment test against a spider mite Placed a seedling made of 1.2 leaves grown in a polypot with a diameter of 4 cm in a receiving dish, and 20 ml of an emulsion diluted in water (100 ppm) prepared according to Formulation Example 1 The original soil surface was irrigated, and seedlings made 1 day after the treatment were inoculated with 10 adult female nymph mite (1 concentration, 2 repetitions). After the treatment, it was kept in a constant temperature room at 25 ° C.
  • the comparative agent A had a miticide rate of 0%.

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Abstract

Le but de la présente invention est de fournir un nouveau dérivé de 1-phénylpipéridine et un agent pharmaceutique agricole/horticole le contenant en tant que composant actif, en particulier un nouveau dérivé de 1-phénylpipéridine utile pour un agent de lutte contre les organismes nuisibles agricoles/horticoles, un agent de lutte contre les tiques/acariens, un agent de lutte contre les nématodes et analogues, ainsi qu'un procédé de production et un procédé d'utilisation de ceux-ci. L'invention concerne un dérivé de 1-phénylpipéridine représenté par la formule, un N-oxyde, ou un sel de celui-ci. [Dans la formule : R représente, par exemple, un groupe alkyle en C1 -6 ou un groupe haloalkyle en C1 -6 ; X représente, par exemple, un groupe alkyle en C1 -6, un groupe haloalkyle en C1 -6, un atome d'halogène ou un groupe cyano ; Y représente, par exemple, un atome d'halogène ; Z représente, par exemple, un groupe haloalkyle en C1 -6 ; n est un nombre entier de 0, 1, ou 2 ; et m est un nombre entier de 1 à 3.]
PCT/JP2018/014409 2017-04-05 2018-04-04 Nouveau dérivé de 1-phénylpipéridine et agent pharmaceutique agricole/horticole le contenant en tant que composant actif WO2018186440A1 (fr)

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