WO1999052882A1 - Derive de 1,2,3-thiadiazole ou son sel et agent antiparasitaire, et procede d'utilisation - Google Patents

Derive de 1,2,3-thiadiazole ou son sel et agent antiparasitaire, et procede d'utilisation Download PDF

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Publication number
WO1999052882A1
WO1999052882A1 PCT/JP1999/001937 JP9901937W WO9952882A1 WO 1999052882 A1 WO1999052882 A1 WO 1999052882A1 JP 9901937 W JP9901937 W JP 9901937W WO 9952882 A1 WO9952882 A1 WO 9952882A1
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group
same
alkyl
substituents
different
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PCT/JP1999/001937
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English (en)
Japanese (ja)
Inventor
Minoru Yamaguti
Masanobu Onishi
Tateki Nishida
Masayuki Morimoto
Kazuyuki Sakata
Kenji Tsubata
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Nihon Nohyaku Co., Ltd.
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Priority to AU31691/99A priority Critical patent/AU3169199A/en
Publication of WO1999052882A1 publication Critical patent/WO1999052882A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/06—1,2,3-Thiadiazoles; Hydrogenated 1,2,3-thiadiazoles

Definitions

  • the present invention relates to a novel 1,2,3-thiadiazole light derivative or a salt thereof useful as a pesticide, particularly a pesticide, an acaricide or a nematicide, a use thereof, and a method of using the same. .
  • Examples of the haloolefin compound having insecticidal activity include JP-A-63-500037, JP-A-2-280, JP-A-2-85267, JP-A-2-134372, and EP 371 925.
  • Japanese Patent Application Laid-Open No. 10-287659 disclose insecticides, acaricides, and nematicides, but 1,2,3-thiadiazos represented by the general formula (I) of the present invention. No description is made on the derivative or its salts.
  • An object of the present invention is to provide a novel pesticide having excellent activity at a low dose.
  • the present inventors have conducted intensive studies to create a novel pest control agent.
  • the 1,2,3-thiadiazol derivative represented by the general formula (I) of the present invention or a salt thereof is described in the literature.
  • a pest control agent which is an undescribed new compound and further comprises the 1,2,3-thiadiazol derivative or a salt thereof as an active ingredient has excellent effect on various pests at a low dose.
  • the inventors have found that the present invention has been completed.
  • the present invention provides a compound represented by the general formula (I):
  • Alkyl group which may be identical or different, one or more substituents which may have on the ring Ariru (d-:) alkoxy (C, - 6) alkyl group, which may be the same or different dates, 1 Heteroaryl groups which may have the above substituents, which may be the same or different, and heteroaryl groups which may have one or more substituents on the ring) alkyl groups, which may be the same or different, 1 A heteroaryloxy which may have the above substituent (s) on the ring) an alkyl group, which may be the same or different, and A heteroaryl (d- 6 ) alkoxy (d- 6 ) alkyl group, which may have a ring, one COR 5 (wherein R 5 is a hydrogen atom, a halogen atom, a hydroxyl group,
  • (C, _ 6 ) represents a heteroaryl group which may have an alkyl group or a substituent. ), 1) alkyl COR s , wherein R 5 is as defined above.
  • R 5 is the same as above.
  • Mono (d- 6 ) alkyl O—C ⁇ R 5 wherein, Re is the same as above.
  • Mono (C — 6 ) alkyl S (O) n R 5 where n is an integer of 0 to 2 and R 5 is the same as above
  • one CSNR 5 R 6 where R 5 and Re are the same as above
  • one Si R s R 6 R 7 wherein, R 5 and R 6 to the same Ku said, R 7 is a hydrogen atom, a halogen atom, arsenic Dorokishiru group, (CI- 6) alkyl group, halo (c had s) alkyl group , (c 2 - 8) alkenyl group, Nono b (c 2 - s) alkenyl Le group, (c 2 - 6) alkynyl, halo (c 2 - 6) alkynyl group, Ariru group or ⁇ Li Ichiru (C shows
  • W represents -S (O) n- (wherein, n is the same as above)
  • X excludes a fluorine atom.
  • halogen atom in the definition of each substituent indicates a chlorine atom, a bromine atom, an iodine atom or a fluorine atom
  • “( ⁇ _ 12 ) alkyl group” refers to a linear, branched or cyclic alkyl group, such as methyl, ethyl, n-propyl, i-propyl, n-butynole, i —Butynole group, sec—butynole group, t-butyl / le group, neopentynole group, 1,2-dimethylpropyl group, n— hexyl group, cyclohexyl group, n— heptyl group, n-octyl group, n —Decyl group, n-dodecyl group and the like.
  • “(C,- ⁇ ) alkyl group which may be the same or different and may have one or more substituents” means that one or more of the hydrogen atoms is replaced by another substituent.
  • a cycloalkyl group such as cyclopropyl Propyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, etc., amino group, mono- or di (C, ⁇ ) alkylamino group (for example, methylamino group, ethylamino group, dimethylamino group, ethylamino group, methyl) Ethylamino, di One n- Buchiruamino group),) alkylcarbonyl group (e.g.
  • alkoxy force carbonyl group e.g., main-butoxycarbonyl group, an ethoxycarbonyl group, t- butoxy aryloxycarbonyl group
  • ⁇ amino carbonyl group mono- or di
  • alkylamino Bruno carbonyl group e.g., methyl ⁇ amino group, such as methyl E chill ⁇ amino carbonitrile group
  • (flicking 6) alkyl Carbonyloxy group for example, methylcarbonyldioxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, i-propylcarboeroxy group, n-butylcarbonyloxy group, i-butylcarbonyloxy group, sec —Butylcarbonyloxy group, t-butylcarbonyloxy group,
  • (C 2 s ) alkenyl group refers to a linear or branched alkenyl group having one or more double bonds, such as a vinyl group, an aryl group, an i-propyl group, an Methyl-2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 3-pentenyl group, 4-hexenyl group, etc.
  • alkynyl group means one or more triple Represents a linear or branched alkynyl group having a bond, for example, an ethynyl group, a 2-propynyl group, a 1-methyl-2-propyl group, a 1-butyl group, a 2-butynyl group, a 3-butynyl group, etc. Show.
  • (C 2 - 8) alkenyl or - As (C 2 6) substituents on an alkynyl group which may be the same or different
  • substituents on an alkynyl group which may be the same or different
  • the “(C 3 _ 8 ) cycloalkyl group” refers to a cyclic alkyl group, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, or the like.
  • substituent on the ring include a halogen atom or a (C ⁇ 6 ) alkyl group (eg, a methyl group, an ethyl group, a butyl group, an n-butyl group, an i-butyl group, a sec-butyl group).
  • At least one substituent which may be the same or different and is selected from a group, a t-butyl group, an n-pentyl group, and an n- hexyl group.
  • Aryl group refers to a phenyl or naphthyl group
  • aryl alkyl group refers to a linear, branched or cyclic alkyl group having a phenyl or naphthyl ring, such as benzyl, phenethyl, It represents phenylpropyl, phenylbutyl, ⁇ -methylbenzyl, ct, ⁇ -dimethylbenzyl and the like
  • aryloxy (C t 6 ) alkyl group means a linear or branched group having a phenyl or naphthyl ring. Represents an oxyalkyl group in the form of “aryl ( ⁇ _ 6 ) alkoxy
  • alkyl group "represents a linear or branched alkoxyalkyl group having phenyl or naphthyl ring.
  • Aryl group "Aryl (d- 6 ) alkyl group”, “Aryloxy (d- 6 ) alkyl group” or "Aryl group”
  • Substituents on the ring of the (C, _ 6 ) alkoxy (C ⁇ ) alkyl group may be the same or different and include a halogen atom, a nitro group, a cyano group, a (d 12 ) alkyl group, a halo (d — 6 ) alkyl group, (d- 6 ) alkoxy group, halo (d) alkoxy group, —S (O) n (d 6 ) alkyl group (where n is an integer of 0 to 2), halo (C -!
  • NR 6 CO Re (R 6 and R 6 are the same as described above), one NR 5 CO NR 6 R 7 (R 6 , R 6 and R 7 are the same as described above), a phenyl group, which may be the same or different.
  • alkyl group having 1 to 5 substituents selected from an alkylaminocarbonyl group, a nitro group, or a cyano group, a phenyloxy group, which may be the same or different, and Androgenic atom, a nitro group, Shiano group, ( ⁇ -5) alkyl group, (C n) alkoxy groups, Nono port (C, - 6) alkyl groups, (CH) haloalkoxy group,
  • Heteroariru group “Heteroariru (d-6) alkyl group”, “heteroaryl Ariruokishi) alkyl group” or “Heteroariru 6) alkoxy (C, - 6) alkyl” and Teroariru to the aromatic heterocyclic group
  • the heterocyclic group includes a compound in which one double bond is reduced and a compound in which a heteroatom atom in an aromatic heterocyclic ring is oxidized.
  • thiazoline to thiazole pyridine to N-pyridine
  • the heterocyclic ring includes, for example, furan, thiophene, pyrroic acid, pyrroline, cyxazonole, oxazoline, isoxazole, thiazole, thiazoline, isothiazol, imidazole, pyrazol, Virazoline, 1,2,4_oxaziazol, 1,3,4-oxaziazol, 1,2,4-thiadiazol, 1,3,4-thiadiazol, 1,2,3-thiadiazole, 1,2,5-thiadiazole, 1,2,3-triazol, 1,2,4-triazole, tetrazole, pyridine, pyrimidine , Pyridazine, pyrazine, oxazine, thiazine, triazine, pyrrofuran, pyrrolofurazan, pyrromid imidazol, pyrropyridine
  • Benzo derivatives include, for example, benzofuran, isobenzofuran, 1-benzothiophene, 2-benzothiophene, indole, isoindole, 1,2-benzothiazole, 1,3-benzothiazole, and 2,1-benzothiazole.
  • Examples of the substituent of the heterocyclic group may be the same or different, a halogen atom, shea Anomoto, human Dorokishi group, (d-8) alkyl groups, halo (C! 6) alkyl group, (C 2 _ 8) alkenyl, halo (C 2 6) alkenyl group, (C 2 6) alkynyl, halo (C 2 6) alkynyl, (C 3 8) cycloalkyl group, (d 6) ⁇ alkoxy group, halo ( C, - 6) alkoxy groups, (C 2 6) Arukeniruokishi group, Nono port (C 2 - 6) Arukeniruokishi group, (d-6) alkoxy (C, - 6) alkyl, (C doctor 6 ) alkylthio groups, halo (d s) alkylthio group, an amino group, 1 or 2 identical or different and good (C, - 6) amino
  • Examples of the salts of the 1,2,3-thiadiazole derivative represented by the general formula (I) of the present invention include inorganic acid salts such as hydrochloride, sulfate, nitrate and phosphate, acetate, fumaric acid and the like.
  • Organic acid salts such as salt, maleate, oxalate, methanesulfonate, benzenesulfonate, paratoluenesulfonate, sodium ion, potassium ion Salts with metal ions such as on and calcium ions can be exemplified.
  • W—CH 2 —CH 2 —CX may be CF 2
  • W is a sulfur atom or a carbonyloxy group
  • X is a hydrogen atom
  • the other substituent is a part of the substituent.
  • a substituent having an aryl or a heteroaryl for example, an aryl group optionally having a substituent, an arylalkyl group optionally having a substituent, an aryloxyalkyl group optionally having a substituent
  • X is a hydrogen atom
  • W is a sulfur atom or a carbonyloxy group
  • the other or R 2 is an aryl group such as a phenyl group, a phenoxymethyl group, a naphthyl group or a pyridyl group
  • a substituted or unsubstituted halogen atom, a (d- 6 ) alkyl group, a halo (d- 6 ) alkyl group, a ( ⁇ ⁇ 6 ) substituents such as alkoxy or halo ( ⁇ Bok O) alkoxy groups are preferred.
  • R substituent at the 4-position of 1,2,3-thiazazole
  • 5-position is R
  • M is sodium or hydrogen
  • L represents an alkali metal atom such as lithium
  • L represents a leaving group such as a chlorine atom, a bromine atom, an iodine atom, an alkylsulfonate group, or an arylsulfonate group
  • n represents an integer of 1 or 2.
  • General formula (Ilia) as a starting compound of the present invention can be produced according to a known method. That is, the compound (Ilia) in which W, is an oxygen atom can be produced according to the method described in Hemushi's Berichte (Chem. Ber., 99, 1618-1631, 1966).
  • the compound (Ilia) that is a sulfur atom is disclosed in
  • the starting compound (Il lb) can be produced according to the method described in European Patent Publication No. EP-25252474.
  • Compounds in which W t is a nitrogen atom are described in Journal of 'The Chemical.
  • the compound represented by the general formula (Ilia) produced according to the above method is reacted with the compound (IV) in the presence or absence of an inert solvent, and in the presence or absence of a base as necessary.
  • a compound represented by the general formula (V) is obtained.
  • the compound represented by the general formula (Ie) can be produced by isolating or not isolating the compound (V) and conducting a bromine elimination reaction in the presence of an inert solvent and a catalyst.
  • the compound (Ie) in which is a sulfur atom among the compounds obtained by the above reaction was oxidized by a conventional method, for example, in an inert solvent in the presence of a suitable oxidizing agent, whereby the sulfur atom was oxidized.
  • Compound (la) ′ can be produced.
  • the reaction is usually carried out in an inert solvent in the presence of a base, and the reaction temperature range varies depending on the reagents used and the reaction solvent, but usually ranges from 180 ° C to 200 ° C. Yes, it is preferably in the range of 120 ° C to 100 ° C. Reaction times are typically from instantaneous to 24 hours.
  • the amount of the reactants used in the reaction is different from the compound (Ilia), but the compound (VI) varies depending on the reactivity, economics and other conditions of the compound. And preferably 0.7 to 1.5 equivalents.
  • the base is usually in a proportion ranging from 1 to 5 equivalents, preferably in a proportion ranging from 1 to 2 equivalents.
  • the reaction can be performed without using a base.
  • Examples of the base used in the reaction include alkali metal alkoxides such as sodium methoxide and potassium tert-butoxide, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, sodium carbonate, and carbonate.
  • Inorganic bases such as alkali metal carbonates such as potassium and sodium bicarbonate; alkali metal hydrides such as sodium hydride and calcium hydride; triethylamine, pyridine; 1,8-diazabicyclo [5.4.0] 7 (hereinafter referred to as DBU), and organic bases such as n-butyllithium and lithium diisopropylamide.
  • inert solvent used in the reaction examples include alcohol solvents such as acetonitrile, methanol, ethanol, etc., glycol solvents such as ethylene glycol, halogenated hydrocarbon solvents such as dichloromethane, toluene, xylene, and chloroform.
  • alcohol solvents such as acetonitrile, methanol, ethanol, etc.
  • glycol solvents such as ethylene glycol
  • halogenated hydrocarbon solvents such as dichloromethane, toluene, xylene, and chloroform.
  • Aromatic solvents such as benzene, ether solvents such as tetrahydrofuran (hereinafter referred to as THF), diethyl ether and the like, polyether solvents such as methyl cello sonolev and ethyl solvent, dimethylformamide ( Hereinafter, amides such as DMF), dimethylacetamide (hereinafter, referred to as DMA), dimethyl sulfoxide (hereinafter, referred to as DMSO), water, and the like. These solvents may be used alone or in combination of two or more, and may be solvent-free.
  • THF tetrahydrofuran
  • DMA dimethylacetamide
  • DMSO dimethyl sulfoxide
  • phase transfer catalyst such as a quaternary ammonium salt such as tetra-n-butylammonium bromide and triethylbenzylammonium chloride, and a crown ether can also be used.
  • reaction is usually carried out in an inert solvent in the presence or absence of a base, and the reaction temperature range varies depending on the reagents and the reaction solvent used, but is usually from 180 ° C to 250 ° C. C, preferably in the range of 120 ° C to 150 ° C. Reaction times typically range from instantaneous to 24 hours.
  • Examples of the base used in the reaction include alkali metal alkoxides such as sodium methoxide and potassium tert-butoxide; alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide; sodium carbonate and potassium carbonate. , Triethylamine, pyridine, DBU, 1,5-diazabicyclo [3.4.0] nonene-5 (hereinafter referred to as DBN), and the like.
  • the amount of the base used depends on the compound (V).
  • the base is usually in a ratio of 1 to 5 equivalents, preferably in a ratio of 1 to 2 equivalents.
  • the inert solvent used in the reaction examples include alcohol solvents such as acetonitrile, methanol, and ethanol; glycol solvents such as ethylene glycol; halogenated hydrocarbon solvents such as dichloromethane; toluene, xylene; Aromatic solvents such as benzene, ether solvents such as THF and diethyl ether, polyether solvents such as methyl-solve and ethyl-solve, amides such as DMF and DMA, DMS ⁇ and water, etc. Is mentioned. These solvents may be used alone or in combination of two or more, and may be solvent-free.
  • phase transfer catalysts such as quaternary ammonium salts such as tetra-n-butylammonium bromide and triethylbenzylammonium chloride, and crown ethers can also be used.
  • Oxidizing agents that can be used in the reaction include, for example, hydrogen peroxide, peracids such as metabenzo-perbenzoic acid and benzoyl peroxide, potassium permanganate, sodium periodate, sodium perborate, and acylated nitrous acid.
  • Inert solvents that can be used include, for example, water, alcohols, glycol solvents, Halogenated hydrocarbon solvents, aromatic solvents and the like can be used. These inert solvents may be used alone or as a mixture of two or more.
  • the desired compound (Ie) can be prepared by reacting the starting compound (XIV) with the compound (XV) in an inert solvent in the presence or absence of a base. ) Can be manufactured.
  • the starting compound (XIV) is available from Heterocycles, Vol. 36, No. 33-36 (1993), Japanese Unexamined Patent Publication No. 59-39884, or the journal “Ob 'Chemical” Society ( 1965) 5166-5176) and the like.
  • the compound (XV) to be reacted can be produced according to the production method disclosed in Japanese Patent Application Laid-Open No. Hei 9-501175. 1-4. Process from compound (XIV) to compound (Ie)
  • reaction temperature range of this reaction varies depending on the reagents and reaction solvents used, etc., but is usually in the range of 78 ° C. to 250 ° C., preferably in the range of 0 ° C. to 150 ° C. It is. Reaction times typically range from instantaneous to 48 hours.
  • the compound represented by the general formula (XV) is in a range of 0.5 to 2 equivalents per 1 equivalent of the compound represented by the general formula (XIV), and is preferably The range is from 0.8 to 1.2 equivalents.
  • This reaction can be carried out in the same manner as in the step from compound (Ilia) to compound (V) to produce the desired product.
  • R 3 is a hydrogen atom
  • (C 1-6 ) represents an alkyl group or a phenyl group which may have a substituent.
  • the compound represented by the above general formula (VII) or ( ⁇ ′), which is the starting compound for this reaction, can be obtained by a known method, that is, JP-A-8-325110 (a compound having 5-position COOH). 'Berichte (Chem. Ber., 99, 1618-1631, 1966) (compounds in which the 4-position is a carboxylic acid derivative and compounds in which the 5-position represents a hydroxyl group, a mercapto group or an amino group), etc.
  • the compound (lb) can be derived by proceeding the reaction according to the conditions disclosed in the above-mentioned patent publications and the like.
  • each reaction may be performed according to the above-mentioned known methods. That is, the compound of the general formula (VII) is represented by the general formula (VIII) by using a suitable halogenating agent such as thionyl chloride and phosphorus oxychloride.
  • a suitable halogenating agent such as thionyl chloride and phosphorus oxychloride.
  • the acid halide is reacted with a compound of the general formula (IX) or (X) in an inert solvent in the presence of a base, usually in the presence of a base, the compound ( lb).
  • a primary amine or an aniline represented by the general formula (XVI) an amide represented by the general formula ( ⁇ ) is produced, and the amide ( ⁇ ⁇ ′) is produced.
  • the compound (lb) can be obtained by reacting the compound (IV) or (VI) with the compound (IV) according to the step of producing (le) from the compound (Ilia) in the above Reaction Scheme 1.
  • a thioamide (If) can be produced by reacting the compound (lb) with a sulfurizing reagent such as a Lawesson reagent.
  • R 4 represents a (C, — 6 ) alkyl group
  • M represents a hydrogen atom or a sodium atom.
  • the compound represented by the above general formula (XI), which is a starting compound of this reaction, is disclosed in JP-A-59-39884, JP-A-Ichiguppa Patent Publication No. EP 104444, etc. Can be produced according to the method described in (1).
  • a base By treating compound (XI) with a base, a mercaptothiadiazole or a salt thereof represented by the general formula (XII) can be produced.
  • the compound (XII) can be isolated or not isolated and reacted with the compound (VI) to produce the compound represented by the general formula (Ic).
  • the process from compound (XI) to compound (Ic) It is carried out in accordance with the conditions disclosed in Japanese Patent Application Laid-Open No. Hei 9-151197, or as follows.
  • reaction is usually carried out in an inert solvent in the presence of a base, and the reaction temperature is usually in the range of 80 ° C to 200 ° C, preferably -20 ° C to 100 ° C, and more preferably 0 ° C to 100 ° C. ° C to room temperature. Reaction times usually range from instantaneous to 24 hours.
  • the amount of the base used in the reaction is usually 1 to 5 mol, preferably 1 to 2 mol, per 1 mol of compound (XI).
  • Examples of the base used in the reaction include inorganic bases such as alkali metal hydroxides such as powdered potassium hydroxide, alkali metal alkoxides such as sodium methoxide, sodium methoxide and potassium t-butoxide; DBU, DBN, etc. Organic bases and the like.
  • inorganic bases such as alkali metal hydroxides such as powdered potassium hydroxide, alkali metal alkoxides such as sodium methoxide, sodium methoxide and potassium t-butoxide; DBU, DBN, etc.
  • inert solvent used in the reaction examples include alcohol solvents such as acetonitrile, methanol and ethanol, glycol solvents such as ethylene glycol, halogenated hydrocarbon solvents such as dichloromethane, toluene, xylene, and chlorobenzene.
  • the amount of the compound (VI) to be subsequently reacted is 0.5 to 2 equivalents, preferably 0.8 to 1.2 equivalents, per 1 equivalent of the compound (XI).
  • Compound (XIII) which is a starting material for this reaction, is generally produced according to the method described in JP-A-59-39884, JP-A-Tsubaki Patent Publication No. EP 104403 or the like. can do.
  • the compound represented by (Id) can be produced.
  • chlorodifluoroacetic acid and a phosphorus compound such as a triarylphosphine such as triphenylphosphine or a trialkylphosphine or a trialkylphosphite form a ylide compound and then react with the aldehyde.
  • a method in which the same reaction is carried out using dibromodifluoromethane This reaction can be carried out according to the method described in Tetrahedron Lett. (Tetrahedron Lett., 23, 1461-1463, 1964), Japanese Patent Publication No. 8-503932, and the like.
  • Me represents methyl
  • E t represents ethyl
  • P r represents propyl
  • Bu represents butyl
  • He x represents hexyl
  • Oct represents octyl
  • Ph “" Indicates phenyl
  • Bn indicates benzyl
  • n- indicates normal
  • i-1 indicates iso
  • t-1 indicates tertiary
  • Me 0 indicates methoxy.
  • I-1 27 1.42 (t, 3H), 2.4-2.5 (ra, 2H), 3. ll (t, 2H),
  • III-1 18 2.4-2.6 (m, 2H), 3.8—3.9 (m, 2H), 4.1—4.3 (m, IH),
  • Pest control agent which is an active ingredient is suitable for various pests such as agriculture, forestry, horticulture, storage pests and sanitary pests, mites and nematodes that infest rice, vegetables, fruit trees, other crops and flowers, etc.
  • apple oysters Adoxophyes orana fasciata
  • cynopods Adoxophyes sp.
  • Apple crocodile Graphol ita inopinata
  • pear ita molesta Graphol ita molesta
  • glyceminola Teyanozuma: ⁇ -(Homona magnaniraa), Chianohosoga (Calopti lia thevivora), Ringohosoga
  • vigintiotopunctata, 7 s Callosobruchus chinensis, Insect beetle (Listroderes costirostris, Scarab beetle (Sitophilus zeamais), Anthonomus gradis gradis, Din; femoral is), Oroema oryzae, Damin (Zeugodacus;
  • insects such as Acaie force (Culex pipiens pipiens), flea beetle (Phyllotreta striolata), and pine beetle
  • Rostochiensis Meloidogyne sp., Tylenchulus semipenetrans, Aphelenchus avenae, Aphelenchoides ritzemabosi, etc. It is. Scientific names are based on agricultural and forestry harmful animals. Insect Directory, 1987 edition (edited by the Japan Society of Applied Animal Entomology).
  • the pesticidal agent of the present invention containing a 123-thiadiazol derivative represented by the general formula (I) or a salt thereof as an active ingredient damages paddy rice, vegetables, fruit trees, other crops, flowers and the like. It has a remarkable insecticidal activity against the above-mentioned pests or sanitary pests. Therefore, before the pests are generated or at the time when the pests are confirmed to occur, the rice and fruit
  • the pest control agent of the present invention can be applied to vegetables, other crops, flowers, etc. by treating paddy water, foliage or soil, etc., and sanitary pests in houses and trenches around houses that damage humans and animals.
  • the present invention is not limited to only these embodiments.
  • a 123-thiadiazol derivative or a salt thereof represented by the general formula (I) of the present invention is used as a pesticide, it is formulated into a convenient form in accordance with a conventional method for pesticide formulation. It is common to use it. That is, the 1,23-thiadiazole derivative compound represented by the general formula (I) of the present invention or a salt thereof can be prepared by adding these to a suitable inert carrier and, if necessary, together with an auxiliary. And dissolving, separating, suspending, mixing, impregnating, and adsorbing it in an appropriate ratio to prepare an appropriate dosage form such as a suspension, emulsion, liquid, wettable powder, granule, powder, tablet, etc. Just use it.
  • the inert carrier that can be used in the present invention may be either solid or liquid.
  • the material that can be a solid carrier include soybean flour, cereal flour, wood flour, bark flour, sawdust, tapako stalk flour. , Walnut powder, bran, cellulose powder, residue after extracting plant extract, crushed synthetic tree Synthetic polymers such as fats, clays (eg, kaolin, bentonite, acid clay), talcs (eg, talc, pyrophyllide, etc.), silicas (eg, diatomaceous earth, silica sand, mica, white carbon, etc.) Synthetic polymer silicic acid, also known as hydrous silicic acid, contains calcium silicate as a main component depending on the product.]), Activated carbon, zeolite powder, pumice, calcined diatomaceous earth, crushed bricks, fly ash, sand, calcium carbonate Examples include inorganic mineral powders, chemical fertilizers such as ammonium sulfate, phospho
  • Materials that can be liquid carriers are selected from those that have a solvent function per se, and those that can disperse the active ingredient with the aid of adjuvants even without the solvent function.
  • Examples thereof include the following carriers, which may be used alone or in the form of a mixture of two or more types. Examples thereof include water, alcohols (eg, methanol, ethanol, isoprono, phenol, and butanol).
  • ethylene glycolone, etc. ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, etc.), ethers (eg, ethyl ether, dioxane, cellosolve, di Propyl ether, tetrahydrofuran, etc.), aliphatic hydrocarbons (eg, kerosene, mineral oil, etc.), aromatic hydrocarbons (E.g., benzene, tosoleene, xylene, sonoleventnaphtha, alequinolenaphthalene, etc.); Ethyl acetate, diisopropyl phthalate, dibutyl phthalate, dioctyl phthalate, etc., amides (eg, dimethylformamide, getylformamide, dimethylacetamide, etc.), nitriles (eg.,
  • Surfactants are used for the purpose of emulsifying, dispersing, solubilizing and / or wetting the active ingredient compounds, such as polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene higher fatty acid ester, Xyethylene resin acid ester, polyoxyethylene sorbitan monolaurate, Examples thereof include surfactants such as polyoxyethylene sorbitan monooleate, alkylaryl sulfonate, naphthalene sulfonic acid condensate, lignin sulfonate, and higher alcohol sulfate ester.
  • auxiliaries For the purpose of stabilizing the dispersion of the active ingredient compound, sticking and Z or bonding, the following auxiliaries can be used.
  • auxiliaries for example, casein, gelatin, starch, methylcellulose, carboxymethylcellulose, gum arabic
  • auxiliary agents such as polyvial alcohol, pine oil, bran oil, bentonite, and ligninsulfonate can also be used.
  • auxiliaries can be used to improve the flowability of solid products.
  • auxiliaries such as wax, stearate, alkyl phosphate and the like can be used.
  • an auxiliary agent such as a naphthalenesulfonic acid condensate and a condensed phosphate may be used.
  • an antifoaming agent for example, an auxiliary agent such as silicone oil can be used.
  • the compounding ratio of the active ingredient compound can be adjusted according to need. For example, 0.01 to 50% by weight in the case of powder or granules, and 0 in the case of emulsion or wettable powder. 0.1 to 50% by weight is suitable.
  • the pesticidal agent of the present invention is used for controlling various pests, as it is, or in an appropriately diluted or suspended form with water or the like, in an amount effective for pest control in crops in which the occurrence of the pest is predicted. Alternatively, it may be applied to a place where generation is not preferable.
  • the amount of the pest control agent of the present invention depends on various factors, for example, the purpose, the target pest, the growth status of the crop, the tendency of the pest, the weather environment condition, the dosage form, the method of application, the place of application, the time of application, etc. Although it fluctuates, the active ingredient compound may be appropriately selected from the range of 0.01 g to 5 kg per 10 ares according to the purpose.
  • the pesticidal agent of the present invention can be further used in combination with other agricultural or horticultural insecticides or fungicides for the purpose of extending pests to be controlled, suitable period of control, or reducing the amount of drugs. .
  • Example 1 Preparation of 4- (4-chlorophenyl) -15- (4,4-difluorobut-3-enylthio) —1,2,3-thiadiazole (Compound No. 1-15) Preparation of sodium methoxide. 5 N methanol solution 10 ml at room temperature, ⁇ 4- (4-chlorophenyl) -1,2,3-thiadiazole 5-yl ⁇ thio ⁇ methyl propionate 1.57 g (5 mmol) was added dropwise.
  • the reaction mixture was poured into water, extracted twice with ethyl acetate, washed once with a saturated saline solution, dried over anhydrous sodium sulfate, and the solvent was distilled off.
  • the resulting brown liquid was purified by silica gel chromatography to obtain 1.11 g (78% yield) of the desired product as a colorless oil.
  • parts means “parts by weight”.
  • the above is uniformly mixed and pulverized to obtain a powder.
  • the above is uniformly mixed and pulverized to obtain a wettable powder.
  • Test example 1 Insecticidal effect test against Japanese moth (Plutel la xylostel la)
  • the Chinese cabbage seedlings produced by the Japanese Conger eggs are immersed in a chemical solution diluted to 50 ppm with the drugs containing the compounds listed in Tables 1 to 5 as active ingredients for 30 seconds, air-dried, and then placed in a plastic container. It was stoppered and stored in a constant temperature room at 25 ° C. Processing investigate death number insects after 6 days, to calculate the mortality from the following equation, c 1 ° 2 0 mice that were determined according to criteria below. Two consecutive.
  • Test example 2 Insecticidal effect test on brown squid (Ni laparvata lugens)
  • a preparation containing the compounds described in Tables 1 to 5 of the present invention as active ingredients is dispersed in water and diluted to a drug solution of 500 ppm, and rice seedlings (variety: Nipponbare) are immersed in the drug solution for 30 seconds. After air-drying, they were placed in a glass test tube, inoculated with 10th instar larvae of the three-instar larvae, and then cotton-plugged and stored in a constant temperature room at 25 ° C. Eight days after the inoculation, the number of live and dead insects was examined, and the mortality was calculated by the following formula. Untreated plot survival rate-treated plot survival rate
  • Test example 4 Insecticidal effect test on Satsuma Moneko-Senyu (Meloidogyne incognita)
  • a chemical solution prepared by diluting a compound containing the compounds shown in Tables 1 to 5 to 50 ppm with water is irrigated into the seedlings of the seedlings of corn soybeans grown in pots in a greenhouse.
  • the number of root nodules was examined, and compared with the number of root nodules in the untreated group, and judged according to the following criteria.
  • Blank Number of nodules equal to or greater than that of the untreated area
  • AAAA 1 AACA 2 AADA 3 AAAA 4 AABA 5 AA 6 AAAA 7 AACA 8 AA 9 AAAA 10 AAAA 11 AA 12 AAA 13 AAAA
  • Test example 1 Compound number Test example 1. Test example 2. Test example 3. Test example 4.
  • III-4 A A A III-5 A A
  • III-6 A A III-7 A A A 111-12 C A III-14 A
  • III- 18 A A III- 19 C C

Abstract

L'invention porte sur un dérivé de 1,2,3-thiadiazole représenté par la formule générale (I) dans laquelle R1 ou R2 représente W-CH2-CH2-C(X)=CF2, W représentant -O-, -S(O)n- où n vaut entre 0 et 2, -C(=Z)-Y où Z représente O ou S, Y représente O, S, NR3 où R3 représente H ou un alkyle, ou bien NR4 où R4 représente H ou un alkyle, X représente H ou F, et l'un ou l'autre de R1 et R2 représente H, un halogène, un cyano, un alkyle substitué ou non substitué, un alcényle, un alkynyle, un cycloalkyle, un aryle, un arylalkyle, un hétéroaryle, un hétéroarylalkyle ou analogue, ou un sel de celui-ci. L'invention porte également sur un agent antiparasitaire comprenant le composant précité agissant comme ingrédient actif, et sur son procédé d'utilisation.
PCT/JP1999/001937 1998-04-13 1999-04-12 Derive de 1,2,3-thiadiazole ou son sel et agent antiparasitaire, et procede d'utilisation WO1999052882A1 (fr)

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AU31691/99A AU3169199A (en) 1998-04-13 1999-04-12 1,2,3-thiadiazole derivative or salt thereof and pest control agent, and method of use thereof

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JP10/117869 1998-04-13
JP11786998 1998-04-13

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WO2002006259A1 (fr) * 2000-07-13 2002-01-24 Bayer Cropscience Ag Thioethers de fluoralcenyle heterocycliques et utilisation en tant que pesticides (iv)
US6743814B2 (en) 2000-03-09 2004-06-01 Nihon Bayer Agrochem K.K. Nematicidal trifluorobutenes
US6908937B2 (en) 2000-07-13 2005-06-21 Bayer Cropscience Ag Heterocyclic fluoroalkenyl thioethers (II)
US6927215B2 (en) 2000-07-13 2005-08-09 Bayer Cropscience Ag Heterocyclic fluoroalkenyl thioethers and the use thereof as pesticides (I)
CN103214476A (zh) * 2013-05-02 2013-07-24 南开大学 一类含4-甲基-1,2,3-噻二唑的甲脒衍生物及其制备方法和用途
CN103214475A (zh) * 2013-05-02 2013-07-24 南开大学 一类含4-甲基-1,2,3-噻二唑的α-(取代)羟基酰胺衍生物及其制备方法和用途
CN103214432A (zh) * 2013-05-02 2013-07-24 南开大学 基于5-甲基-1,2,3-噻二唑的α-(取代)羟基酰胺衍生物及其制备方法和用途
CN103232448A (zh) * 2013-05-02 2013-08-07 南开大学 一类含4-甲基-1,2,3-噻二唑的4,5-二氢噻唑醇酸酯衍生物及其制备方法和用途
WO2013180193A1 (fr) 2012-05-31 2013-12-05 住友化学株式会社 Composé hétérocyclique condensé
WO2017002100A1 (fr) * 2015-09-23 2017-01-05 Isagro S.P.A. Composés de trifluoroalcényle hétérocycliques présentant une activité nématocide, leurs compositions agronomiques et utilisation associée
CN109574956A (zh) * 2017-09-29 2019-04-05 沈阳中化农药化工研发有限公司 一种噻二唑酰胺类化合物及其应用
IT201800004120A1 (it) * 2018-03-30 2019-09-30 Isagro Spa Esteri di composti eterociclici ad attività nematocida, loro composizioni agronomiche e relativo uso
WO2019189731A1 (fr) * 2018-03-30 2019-10-03 住友化学株式会社 Composé hétérocyclique et agent de lutte contre les arthropodes nuisibles le contenant

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JPH05271172A (ja) * 1991-11-01 1993-10-19 Ciba Geigy Ag 酪酸誘導体
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US6743814B2 (en) 2000-03-09 2004-06-01 Nihon Bayer Agrochem K.K. Nematicidal trifluorobutenes
US6710045B2 (en) 2000-07-13 2004-03-23 Bayer Cropscience Ag Heterocyclic fluoroalkenyl thioethers and the use thereof as pesticides (IV)
US6908937B2 (en) 2000-07-13 2005-06-21 Bayer Cropscience Ag Heterocyclic fluoroalkenyl thioethers (II)
US6927215B2 (en) 2000-07-13 2005-08-09 Bayer Cropscience Ag Heterocyclic fluoroalkenyl thioethers and the use thereof as pesticides (I)
WO2002006259A1 (fr) * 2000-07-13 2002-01-24 Bayer Cropscience Ag Thioethers de fluoralcenyle heterocycliques et utilisation en tant que pesticides (iv)
WO2013180193A1 (fr) 2012-05-31 2013-12-05 住友化学株式会社 Composé hétérocyclique condensé
CN104334552B (zh) * 2012-05-31 2016-08-31 住友化学株式会社 稠合杂环化合物
US9120792B2 (en) 2012-05-31 2015-09-01 Sumitomo Chemical Company, Limited Fused heterocyclic compound
CN104334552A (zh) * 2012-05-31 2015-02-04 住友化学株式会社 稠合杂环化合物
CN103232448B (zh) * 2013-05-02 2016-03-30 南开大学 一类含4-甲基-1,2,3-噻二唑的4,5-二氢噻唑醇酸酯衍生物及其制备方法和用途
CN103232448A (zh) * 2013-05-02 2013-08-07 南开大学 一类含4-甲基-1,2,3-噻二唑的4,5-二氢噻唑醇酸酯衍生物及其制备方法和用途
CN103214432B (zh) * 2013-05-02 2015-08-26 南开大学 基于5-甲基-1,2,3-噻二唑的α-(取代)羟基酰胺衍生物及其制备方法和用途
CN103214432A (zh) * 2013-05-02 2013-07-24 南开大学 基于5-甲基-1,2,3-噻二唑的α-(取代)羟基酰胺衍生物及其制备方法和用途
CN103214475B (zh) * 2013-05-02 2016-01-20 南开大学 一类含4-甲基-1,2,3-噻二唑的α-(取代)羟基酰胺衍生物及其制备方法和用途
CN103214475A (zh) * 2013-05-02 2013-07-24 南开大学 一类含4-甲基-1,2,3-噻二唑的α-(取代)羟基酰胺衍生物及其制备方法和用途
CN103214476A (zh) * 2013-05-02 2013-07-24 南开大学 一类含4-甲基-1,2,3-噻二唑的甲脒衍生物及其制备方法和用途
IL258285A (en) * 2015-09-23 2018-05-31 Isagro Spa Heterocyclic trifluoroalkylene compounds having nematocidal activity, agronomic preparations and uses
ITUB20153829A1 (it) * 2015-09-23 2017-03-23 Isagro Spa Composti eterociclici trifluoroalchenilici ad attivita nematocida, loro composizioni agronomiche e relativo uso
WO2017002100A1 (fr) * 2015-09-23 2017-01-05 Isagro S.P.A. Composés de trifluoroalcényle hétérocycliques présentant une activité nématocide, leurs compositions agronomiques et utilisation associée
CN108471752A (zh) * 2015-09-23 2018-08-31 伊萨格罗股份公司 具有杀线虫活性的杂环三氟烯基化合物、其农学组合物及其应用
JP2018535193A (ja) * 2015-09-23 2018-11-29 イサグロ エス．ピー．エー． 殺線虫活性を有する複素環トリフルオロアルケニル化合物、その農学組成物、及びその使用
EA033156B1 (ru) * 2015-09-23 2019-09-30 Исагро С.П.А. Гетероциклические трифторалкенильные соединения с нематоцидной активностью, агрохимические композиции на их основе и их применение
CN109574956A (zh) * 2017-09-29 2019-04-05 沈阳中化农药化工研发有限公司 一种噻二唑酰胺类化合物及其应用
CN109574956B (zh) * 2017-09-29 2023-04-07 沈阳中化农药化工研发有限公司 一种噻二唑酰胺类化合物及其应用
IT201800004120A1 (it) * 2018-03-30 2019-09-30 Isagro Spa Esteri di composti eterociclici ad attività nematocida, loro composizioni agronomiche e relativo uso
WO2019189731A1 (fr) * 2018-03-30 2019-10-03 住友化学株式会社 Composé hétérocyclique et agent de lutte contre les arthropodes nuisibles le contenant
WO2019186498A1 (fr) * 2018-03-30 2019-10-03 Isagro S.P.A. Esters de composés hétérocycliques ayant une activité nématicide, leurs compositions agronomiques et leur utilisation
JPWO2019189731A1 (ja) * 2018-03-30 2021-04-22 住友化学株式会社 複素環化合物及びそれを含有する有害節足動物防除組成物
US11779018B2 (en) 2018-03-30 2023-10-10 Sumitomo Chemical Company, Limited Heterocyclic compound and arthropod pest control composition containing same

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