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WO1995030657A1 - Tetrahydropyrazoles substitues utilises comme agents de lutte contre les parasites - Google Patents

Tetrahydropyrazoles substitues utilises comme agents de lutte contre les parasites Download PDF

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Publication number
WO1995030657A1
WO1995030657A1 PCT/EP1995/001537 EP9501537W WO9530657A1 WO 1995030657 A1 WO1995030657 A1 WO 1995030657A1 EP 9501537 W EP9501537 W EP 9501537W WO 9530657 A1 WO9530657 A1 WO 9530657A1
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Prior art keywords
alkyl
formula
optionally substituted
alkoxy
chlorine
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PCT/EP1995/001537
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German (de)
English (en)
Inventor
Rainer Fuchs
Christoph Erdelen
Andreas Turberg
Norbert Mencke
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Bayer AG
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Bayer AG
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Priority to AU23460/95A priority Critical patent/AU2346095A/en
Publication of WO1995030657A1 publication Critical patent/WO1995030657A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/16—Halogen atoms or nitro radicals

Definitions

  • the present invention relates to new substituted tetrahydropyrazoles, processes for their preparation and their use as pesticides, in particular as insecticides.
  • R 1 represents in each case optionally substituted aryl or hetaryl
  • R 2 represents a five- or six-membered, optionally substituted and optionally benzo-fused heterocycle containing one to four nitrogen atoms
  • R 3 and R 4 independently of one another represent hydrogen or represent in each case optionally substituted by halogen alkyl, alkylcarbonyl, alkoxycarbonyl, alkylsulfonyl, mono- or dialkylaminocarbonyl or
  • R 3 and R 4 together represent the radical A, where
  • R 6 represents hydrogen or alkyl
  • R 5 for each optionally substituted alkyl or cycloalkyl or for the rest
  • R and R 8 independently of one another for hydrogen, halogen, nitro, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, in each case optionally substituted aryloxy or arylthio, optionally substituted mono- or dialkylamino, optionally substituted cycloalkyl, for alkoxycarbonyl, alkenyl, Alkynyl, alkylthionyl, alkylsulfonyl, haloalkylthionyl, haloalkylsulfonyl or haloalkoxycarbonyl or wherein
  • R 7 and R 8 together stand for optionally containing one or two oxygen atoms and optionally substituted alkanediyl and
  • X represents oxygen or sulfur.
  • the compounds of the formula (I) can be present as geometric and / or optical isomers or isomer mixtures of different compositions. The invention relates to both the pure isomers and the isomer mixtures.
  • R 1 , R 2 , R 4 , R 5 and X have the meaning given above, in the presence of a reducing agent, optionally in the presence of a catalyst and in the presence of a
  • R 3 has the meaning given above with the exception of hydrogen, is obtained if the compounds of the above formula (Ia) in which R 1 , R 2 , R 4 , R 5 and X have the meaning given above, with compounds of the formula (III)
  • Hai represents halogen, especially chlorine, bromine or iodine, in the presence of a diluent and, if appropriate, in the presence of a base, and that
  • R 3 and R 4 together represent the radical A, ie the new compounds of the formula (Ib)
  • R 6 has the meaning given above in the presence of an acid and, if appropriate, in the presence of a diluent, and ⁇ ) to give compounds of the formula (Ib) in which A is -CO- or - COCO-, compounds of the formula (Ic)
  • R 1 , R 2 , R 5 and X have the meaning given above, with phosgene or with oxalyl chloride, if appropriate in the presence of a diluent and if appropriate in the presence of a base, and ⁇ ) to obtain compounds of the formula (Ib) in which A is is, compounds of the formula (Id) (obtainable from
  • the tetrahydropyrazoles according to the invention are generally defined by the formula (I).
  • R 1 preferably represents optionally halogen-, nitro, cyano, C 1 - C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkyl, C 1 -C 6 - haloalkoxy, C 1 -C 6 haloalkylthio, C 1 -C 6 -alkoxycarbonyl or di- C 1 - C 6 alkylamino substituted pyridyl, pyrazinyl, pyridazinyl, thienyl,
  • Y and Z are independently hydrogen, halogen, nitro, cyano, C 1 -C 6 - alkyl, C 1 -C 6 alkoxy, C 1 -C 6 -alkylthio, C 1 -C 6 haloalkyl, C 1 - C 6 haloalkoxy, C 1 -C 6 haloalkylthio, C 1 -C 6 alkoxycarbonyl, C 1 -C 8 haloalkoxycarbonyl, each optionally by halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkyl substituted phenoxy or phenylthio, for C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 4 alkylthionyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 -Halogenalkylthionyl, C 1
  • R 2 preferably represents a heterocyclic radical from the series
  • R 9 and R 10 are independently hydrogen, halogen, cyano, nitro, C 1 -C 6 - alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkylthio, C 1 -C 6 alkoxycarbonyl or di (C 1 -C 4 alkyl) amino.
  • R 3 and R 4 are, independently of one another, preferably hydrogen or C 1 -C 5 alkyl, C 1 -C 5 alkylcarbonyl, C 1 -C 5 alkoxycarbonyl, C 1, each optionally substituted by fluorine, chlorine and / or bromine -C 5 alkylsulfonyl, mono- or di- (C 1 -C 5 alkyl) aminocarbonyl or R 3 and R 4 together preferably represent the radical A, where
  • R 6 preferably represents hydrogen or C 1 -C 4 alkyl.
  • R 5 preferably is optionally substituted by halogen or C 1 -C 4 -haloalkoxy-substituted C 1 -C 8 - alkyl, optionally substituted by halogen, C 1 -C 4 - haloalkyl or C 1 -C 4 -haloalkoxy-substituted C 3 -C 7- cycloalkyl or for the rest
  • R 7 and R 8 independently of one another are hydrogen, halogen, nitro, cyano, C 1 -C 8 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 - alkylthio, C 1 -C 8 haloalkylthio, each for phenoxy or phenylthio, each optionally substituted by halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or C 1 -C 8 haloalkyl, for each mono- or di- (C 1 -C 6 -alkyl) amino optionally substituted by halogen, C 1 -C 4 -alkoxy or C 1 -C 4 -haloalkoxy, for optionally substituted by halogen, C 1 -C 4 -alkyl, C.
  • X preferably represents oxygen or sulfur.
  • R 1 particularly preferably represents the rest
  • Y and Z are independently hydrogen, fluorine, chlorine, bromine, nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 3 alkylthio, C 1 -C 3 haloalkyl , C 1 -C 3 - halogenoalkoxy, C 1 -C 3 haloalkylthio, C 1 -C 3 alkoxycarbonyl, C 1 -C 3 - haloalkoxycarbonyl, represents optionally fluorine-, chlorine-, bromine-, C 1 -C 3 alkyl , C 1 -C 3 alkoxy or C 1 -C 3 haloalkyl substituted phenoxy or phenylthio, for C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 3 alkylthionyl, C 1 -C 3- alkylsulfonyl, C 1 -C 3
  • R 2 particularly preferably represents a heterocyclic radical from the series
  • R 9 and R 10 independently represent hydrogen, chlorine, bromine, methyl, ethyl or trifluoromethyl.
  • R 3 and R 4 independently of one another particularly preferably represent hydrogen or C 1 -C 4 alkyl, C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl, C 1 - each optionally substituted by fluorine and / or chlorine.
  • R 3 and R 4 together are particularly preferably the radical A, where
  • R 6 particularly preferably represents hydrogen or C 1 -C 3 alkyl.
  • R 5 particularly preferably represents C 1 -C 4 alkyl optionally substituted by fluorine, chlorine, bromine or C 1 -C 3 haloalkoxy, and optionally represents fluorine, chlorine, bromine, C 1 -C 8 haloalkyl or C 1 - C 3 haloalkoxy substituted C 3 -C 6 cycloalkyl or for the rest
  • R 7 and R 8 independently of one another are hydrogen, fluorine, chlorine, bromine, nitro, cyano, C 1 -C 4 alkyl, C 1 -C 3 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 3 - Haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 3 haloalkylthio, for optionally by fluorine, chlorine, bromine, C 1 -C 3 alkyl, C 1 -C 3 alkoxy or C 1 -C 3 haloalkyl substituted phenoxy, for mono- or di- (C 1 -C 4 alkyl) amino optionally substituted by fluorine, chlorine, bromine, C 1 -C 3 alkoxy or C 1 -C 3 haloalkoxy, for optionally substituted by fluorine, Chlorine, bromine, C 1 -C 3 alkyl, C 1 -C 3 alkoxy or C 1 -C 3 halo
  • X particularly preferably represents oxygen or sulfur.
  • R 1 very particularly preferably represents the rest
  • Y and Z independently of one another represent hydrogen, fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 3 haloalkyl or C 1 -C 3 haloalkoxy or
  • R 2 very particularly preferably represents a heterocyclic radical from the series
  • R 3 and R 4 independently of one another very particularly preferably represent hydrogen or methyl, ethyl, propyl, methylcarbonyl, ethyl carbonyl, methoxycarbonyl or ethoxycarbonyl or each optionally substituted by fluorine and / or chlorine
  • R 3 and R 4 together very particularly preferably represent a radical A, where
  • R 5 very particularly preferably represents C 3 -C 6 -cycloalkyl optionally substituted by C 1 -C 3 haloalkyl or the rest
  • R 7 and R 8 are each independently hydrogen, cyano, nitro, fluorine, chlorine, bromine, C 1 -C 4 - alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 - Halogenalkoxy, C 1 -C 3 haloalkylthio or for C 1 -C 3 haloalkylsulfonyl or
  • X very particularly preferably represents oxygen.
  • substituents halogenoalkyl in the radicals haloalkyl, haloalkoxy, haloalkylthio, haloalkylthionyl and haloalkylsulfonyl preferably contains 1 to 9, particularly preferably 1 to 7 and very particularly preferably 1 to 5 identical or different halogen atoms, fluorine, chlorine and bromine being particularly preferred as halogen atoms, and very particularly Fluorine and chlorine are preferred.
  • Formula (II) provides a general definition of the dihydropyrazoles required as starting materials for carrying out process A according to the invention.
  • R 1 , R 2 , R 4 , R 5 and X preferably or particularly preferably represent those radicals which are preferred or particularly preferred in connection with the description of the substances of the formula (I) according to the invention for these substituents.
  • the compounds of the formula (II) are known or can be obtained by known processes (cf., for example, EP-A-438 690 and EP-A-490 569).
  • Formula (Ia) provides a general definition of the tetrahydropyrazoles required as starting materials for carrying out process B according to the invention.
  • R 1 , R 2 , R 4 , R 5 and X preferably or particularly preferably represent those radicals which are preferred or particularly preferred in connection with the description of the substances of the formula (I) according to the invention for these substituents.
  • the compounds of the formula (Ia) are new and can be obtained by process A according to the invention.
  • the compounds of formula (III) which are also required as starting materials for carrying out process B according to the invention are generally known compounds of organic chemistry.
  • Formula (Ic) provides a general definition of the tetrahydropyrazoles required as starting materials for carrying out processes C ⁇ and Cß according to the invention.
  • R 1 , R 2 , R 5 and X preferably or particularly preferably represent those radicals which, in connection with the description of the substances of the formula (I) according to the invention, are preferred or particularly preferred for these substituents were called.
  • the compounds of the formula (Ic) are new and can be obtained by the known process A.
  • the aldehydes of the formula (IV) which are also required as starting materials for carrying out the process C ⁇ according to the invention are generally known compounds of organic chemistry.
  • Formula (Id) provides a general definition of the tetrahydropyrazoles required as starting materials for carrying out process C ⁇ according to the invention.
  • R 1 , R 2 , R 5 , R 6 and X preferably or particularly preferably represent those radicals which are preferred or particularly preferred in connection with the description of the substances of the formula (I) according to the invention for these substituents.
  • Process A described above is carried out in the presence of a diluent and in the presence of a reducing agent.
  • Non-protic solvents e.g. Hydrocarbons such as hexane, cyclohexane, benzene, toluene or ethers such as diethyl ether, dioxane, tetrahydrofuran or diethylene glycol dimethyl ether are used.
  • Hydrocarbons such as hexane, cyclohexane, benzene, toluene or ethers such as diethyl ether, dioxane, tetrahydrofuran or diethylene glycol dimethyl ether are used.
  • DIBAL-H diisobutyl aluminum hydride
  • aluminum hydride lithium aluminum hydride
  • sodium borohydride may be mentioned.
  • Hydrogen can also be used as a reducing agent.
  • catalysts for example noble metal catalysts such as e.g. Palladium.
  • protic diluents e.g. Alcohols (methanol, ethanol) can be used.
  • Raney nickel can also be used as a further reducing agent.
  • reaction temperatures can be varied over a wide range in process A. In general, temperatures between -75 ° C and
  • Process A is generally carried out under normal pressure, but it can also be carried out under elevated pressure.
  • the reducing agent and the compound of formula (II) to be reduced are used at least in equimolar amounts, but an up to ten-fold excess of the reducing agent can also be used.
  • Process B described above is carried out in the presence of a diluent and, if appropriate, in the presence of a base.
  • Suitable diluents are all inert organic solvents. These preferably include hydrocarbons such as benzene, toluene, xylene, furthermore ethers such as dibutyl ether, tert-butyl methyl ether, tetrahydrofuran, dioxane, and also polar solvents such as dimethyl sulfoxide, acetonitrile, sulfolane, dimethylformamide and N- Methyl pyrrolidone.
  • hydrocarbons such as benzene, toluene, xylene
  • ethers such as dibutyl ether, tert-butyl methyl ether, tetrahydrofuran, dioxane
  • polar solvents such as dimethyl sulfoxide, acetonitrile, sulfolane, dimethylformamide and N- Methyl pyrrolidone.
  • Alkali metal and alkaline earth metal oxides, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide, magnesium oxide, are preferably usable.
  • Phase transfer catalysts such as e.g. Triethylbenzylammoniumchlorid, Tetrabutylammoniumbromid or 18-Krone-6 can be used.
  • alkali metal and alkaline earth metal amides and hydrides such as sodium amide, sodium hydride and calcium hydride, and also alkali metal alcoholates, such as sodium methylate, sodium ethylate and potassium tert-butoxide, can also be used.
  • reaction temperatures can be varied within a wide range in process B. In general, temperatures between -20 ° C and 200 ° C, preferably between 0 ° C and 150 ° C.
  • Process B is generally carried out under normal pressure, but it can also be carried out under elevated pressure.
  • Process B The starting materials are generally used in process B in at least equimolar amounts, but it is also possible to use the compound of the formula (III) in a larger excess.
  • Process C ⁇ described above is carried out in the presence of an acid and optionally in the presence of a diluent.
  • Organic acids are preferred as acids. Examples include formic acid and acetic acid. Diluents used in the processes C ⁇ , Cß, and C ⁇ are all inert
  • the starting materials of the formulas (Ic) and (IV) are generally used in approximately equimolar amounts, but it is also possible to use a larger excess of the aldehyde of the formula (IV).
  • reaction temperatures can be varied within a wide range in the process C ⁇ . In general, between -10 ° C and 200 ° C, preferably between 10 ° C and 150 ° C.
  • Process C ⁇ described above is preferably carried out in the presence of a base.
  • Amines such as e.g. Triethylamine, diisopropylethylamine, pyridine, N-methyl-pyrrolidone, diazabicyclooctane (DACO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).
  • DACO diazabicyclooctane
  • DBN diazabicyclonones
  • DBU diazabicycloundecene
  • reaction temperatures can be varied within a wide range in the process Cß. In general, temperatures between ⁇ 20 ° C and 100 ° C, preferably between 0 ° C and 80 ° C.
  • Process C ⁇ described above is carried out in the presence of a base.
  • Alkali metal and alkaline earth metal amides or hydrides such as sodium amide, sodium hydride and calcium hydride, and also alkali metal alcoholates such as sodium methylate, sodium ethylate and potassium tert-butoxide are also preferably usable.
  • the reaction temperatures can be varied within a wide range in process C ⁇ . In general, temperatures between -20 ° C and 150 ° C, preferably between 0 ° C and 120 ° C.
  • the base and the compound of the formula (Ic) are used in at least equimolar amounts, but an excess of base can also be used.
  • the compounds of formula (I) according to the invention can be used for pest control.
  • Pests are undesirable animal pests, especially insects, which damage plants or higher animals.
  • the active compounds according to the invention are suitable for combating animal scings, preferably arthropods, in particular insects, which occur in the economy, in forests, in the protection of stocks and materials, and in the hygiene sector, with good plant tolerance and favorable heat bleeding toxicity. They are effective against normally sensitive and resistant species and against all or individual stages of development.
  • the pests mentioned above include:
  • Thysanura e.g. Lepisma saccharina.
  • Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.
  • Heteroptera e.g. Eurygaster spp.
  • Dysdercus intermedius Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
  • Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodoniphasis, spp.
  • Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodoniphasis,
  • Nephotettix cincticeps Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp.
  • Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
  • the active compounds according to the invention can be used for use as insecticides in their commercially available formulations and in the use forms prepared from these formulations in a mixture with other active compounds, such as insecticides, attractants, sterilants, acaricides, nematicides, fungicides regulating substances or herbicides.
  • Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms and others
  • acrinathrin alphamethrin, betacyfluthrin, bifenthrin, Brofenprox, cis-resmethrin,
  • Ethiofencarb Fenobucarb, Fenoxycarb, Isoprocarb, Methiocarb, Methomyl, Metolcarb, Oxamyl, Pirimicarb, Promecarb, Propoxur, Terbam, Thiodicarb, Thiofanox, Trimethacarb, XMC, Xylylcarb,
  • Demeton M Demeton-S-methyl
  • Demeton S Diazinon, Dichlorvos, Dicliphos
  • Buprofezin chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, pyriproxifen, tebufenozide, teflubenzuron, triflumuron,
  • Cloethocarb Disulfoton, Ethophrophos, Etrimphos, Fenamiphos, Fipronil, Fonofos, Fosthiazate, Furathiocarb, HCH, Isazophos, Isofenphos, Methiocarb, Monocrotophos, Nitenpyram, Oxamyl, Phorate, Phoxim, Tothiofosirosphosfosufinfosufosfufufofufuf, fos Thiodicarb, Thiafenox, Azocyclotin, Butylpyridaben, Clofentezine, Cyhexatin, Diafenthiuron, Diethion,
  • Solutions, suspensions, emulsions, powders, pastes and granules are used. They are used in the usual way, e.g. by pouring, spraying, spraying, sprinkling.
  • the active compounds according to the invention can be applied both before and after emergence of the plants.
  • the amount of active ingredient used can vary over a wide range. It essentially depends on the type of effect desired. In general the application rates are between 0.01 and 10 kg of active ingredient per hectare of soil, preferably between 0.05 and 5 kg per ha.
  • the active compounds according to the invention can be converted into the customary formulations, depending on their respective physical and / or chemical properties, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active compound-impregnated natural and synthetic Substances, very fine encapsulations in polymeric substances and in coating compositions for seeds, also in formulations with fuel sets, such as smoking cartridges, cans, spirals, etc., as well as ULV cold and warm fog formulations.
  • formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents.
  • extenders that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • surface-active agents that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • water e.g. organic solvents can also be used as auxiliary solvents.
  • aromatics such as xylene, toluene or alkylnaphthalenes
  • chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorothylenes or methylene chloride
  • aliphatic hydrocarbons such as cyclohexane or paraffins, e.g.
  • Petroleum fractions alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water;
  • liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; as solid carriers are possible: e.g. natural rock meals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock meals such as highly disperse silica,
  • Solid carrier materials for granules are suitable: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stems;
  • Possible emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates;
  • Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate and natural phospholipids such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper,
  • Cobalt, molybdenum and zinc can be used.
  • the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • active compounds according to the invention act not only against plant, hygiene and stored product pests, but also in the veterinary sector against ectoparasites such as shield ticks, leather ticks, space mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, featherlings and fleas. For example, they show excellent effectiveness against ticks, such as Boophilus microplus.
  • the active compounds of the formula (I) according to the invention are also suitable for combating arthropods which are farm animals, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as dogs, cats, house birds, aquarium fish and so-called experimental animals such as hamsters, Infest guinea pigs, rats and mice.
  • arthropods are farm animals, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as dogs, cats, house birds, aquarium fish and so-called experimental animals such as hamsters, Infest guinea pigs, rats and mice.
  • the active compounds according to the invention are used in a known manner by enteral administration in the form of, for example, tablets, capsules, drinkers, drenches, granules, pastes, boluses, the feed-through method, suppositories, by parenteral administration, such as, for example, by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.),
  • Implants by nasal application, by dermal application in the form of, for example, diving or bathing (dipping), spraying (spray), pouring on (pour-on and spot-on), washing, powdering and with the help of active substance-containing forin bodies such as collars , Ear tags, tail tags, limb bands, holsters, marking devices, etc.
  • active substance-containing forin bodies such as collars , Ear tags, tail tags, limb bands, holsters, marking devices, etc.
  • the present invention thus also relates to the compounds of the general formula (I) for use as ectoparasiticides and the use of the compounds of the general formula (I) for the preparation of an agent for controlling ectoparasites.
  • Ready-to-use preparations contain the active substance in concentrations of
  • Preparations that are diluted before use contain the active ingredient in concentrations of 0.5-90 percent by weight, preferably 5 to 50 percent by weight. In general, it has been found advantageous to use amounts from about 1 to about
  • mixtures of isomers (cis / trans position of the substituents in the 3- and 4-position of the tetrahydropyrazole ring) can arise during the reduction, which in some cases were separated.
  • the isomers are then referred to as isomer A and isomer B without an exact assignment to the ice or trans form.
  • 35 g of 3 (4'-chlorophenyl) -4- (1 "H-4" -chloropyrazole-l "-yl) -4,5-dihydro-1-pyrazolecarboxylic acid- (4-trifluoromethoxy) anilide are treated under protective gas (argon) dissolved in 400 ml of anhydrous THF, 170 ml (corresponding to 170 mmol) of diisobutylaluminum hydride (DIBAL-H) in n-hexane are added dropwise over the course of 60 minutes at -70 ° C. The mixture is then stirred at 0 ° C.
  • DIBAL-H diisobutylaluminum hydride
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with horseradish leaf beetle larvae (Phaedon cochleariae) while the leaves are still moist.
  • the kill is determined in%. 100% means that all beetle larvae have been killed; Means 0%; that no beetle larvae were killed.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Cabbage leaves (Brassica oleracea) are treated by dipping into the active ingredient preparation of the desired concentration and with caterpillars of the cabbage cockroach
  • the kill is determined in%. 100% means that all caterpillars have been killed; Means 0%; that no caterpillars were killed. In this test, e.g. the compounds according to the preparation examples
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Soybean shoots (Glycine max) are treated by dipping into the active ingredient preparation of the desired concentration and populated with the tobacco bud caterpillar (Heliothis virescens) while the leaves are still moist.
  • the kill is determined in%. 100% means that all caterpillars have been killed; Means 0%; that no caterpillars were killed. In this test, e.g. the compounds according to the preparation examples
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Rice seedlings (Oryza sativa) are treated by dipping into the active ingredient preparation of the desired concentration and populated with the green rice leafhopper (Nephotettix cincticeps) while the leaves are still moist.
  • the kill is determined in%. 100% means that all cicadas have been killed; Means 0%; that no cicadas were killed. In this test, e.g. the compounds according to the preparation examples
  • Test animals Musca domestica, strain WHO (N)
  • a suitable formulation three parts by weight of active ingredient are mixed with seven parts of the solvent-emulsifier mixture mentioned above, and the emulsion concentrate thus obtained is diluted with water to the concentration desired in each case. 2 ml of this active ingredient preparation are pipetted onto filter paper disks (0 9.5 cm), which are located in petri dishes of the appropriate size. After the filter discs have dried, 25 test animals are transferred to the Petri dishes and covered.
  • the effectiveness of the active ingredient preparation is determined. The effectiveness is expressed in%. 100% means that all flies have been killed; 0% means that no flies have been killed.
  • a suitable formulation three parts by weight of active compound are mixed with seven parts of the solvent / emulsifier mixture mentioned above, and the emulsion concentrate thus obtained is diluted with water to the concentration desired in each case. 2 ml of this active ingredient preparation are pipetted onto filter paper disks (0 9.5 cm), which are located in petri dishes of the appropriate size. After the filter discs have dried, 5 test animals P. americana are transferred and covered.
  • the effectiveness of the active ingredient preparation is determined. 100% means that all cockroaches have been killed; 0% means that no cockroaches have been killed.
  • Test animals Lucilia cuprina larvae

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

Abstract

L'invention concerne de nouveaux tétrahydropyrazoles substitués de la formule (I) dans laquelle R1 désigne aryle ou hétaryle éventuellement substitué, R22 désigne un hétérocycle à cinq ou six chaînons, contenant entre un et quatre atomes d'azote, éventuellement substitué et éventuellement benzo-condensé, et R?3, R4, R5¿ et X ont la notation mentionnée dans la description. L'invention concerne par ailleurs des procédés de préparation de ces composés et leur utilisation comme agents de lutte contre les parasites.
PCT/EP1995/001537 1994-05-06 1995-04-24 Tetrahydropyrazoles substitues utilises comme agents de lutte contre les parasites Ceased WO1995030657A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU23460/95A AU2346095A (en) 1994-05-06 1995-04-24 Substituted tetrahydropyrazoles as pest control agents

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19944416112 DE4416112A1 (de) 1994-05-06 1994-05-06 Substituierte Tetrahydropyrazole
DEP4416112.3 1994-05-06

Publications (1)

Publication Number Publication Date
WO1995030657A1 true WO1995030657A1 (fr) 1995-11-16

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PCT/EP1995/001537 Ceased WO1995030657A1 (fr) 1994-05-06 1995-04-24 Tetrahydropyrazoles substitues utilises comme agents de lutte contre les parasites

Country Status (3)

Country Link
AU (1) AU2346095A (fr)
DE (1) DE4416112A1 (fr)
WO (1) WO1995030657A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003010148A1 (fr) * 2001-07-20 2003-02-06 Bayer Cropscience Ag Derives de pyrazoline et leur utilisation comme agents de lutte contre les parasites

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10205057A1 (de) 2002-02-07 2003-08-14 Bayer Cropscience Ag Substituierte 4-Hetaryl-pyrazoline
DE10206791A1 (de) 2002-02-19 2003-08-28 Bayer Cropscience Ag Substituierte 4-Pyrazolyl-pyrazoline

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0438690A2 (fr) * 1990-01-24 1991-07-31 Bayer Ag Dérivés substitués de pyrazoline
US5109014A (en) * 1990-12-10 1992-04-28 Jacobson Richard M N-aryl-3-aryl-4-substituted-2,3,4,5-tetrahydro-1H-pyrazole-1-carboxamides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0438690A2 (fr) * 1990-01-24 1991-07-31 Bayer Ag Dérivés substitués de pyrazoline
US5109014A (en) * 1990-12-10 1992-04-28 Jacobson Richard M N-aryl-3-aryl-4-substituted-2,3,4,5-tetrahydro-1H-pyrazole-1-carboxamides

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003010148A1 (fr) * 2001-07-20 2003-02-06 Bayer Cropscience Ag Derives de pyrazoline et leur utilisation comme agents de lutte contre les parasites

Also Published As

Publication number Publication date
DE4416112A1 (de) 1995-11-09
AU2346095A (en) 1995-11-29

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