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EP0846099A1 - 4,4-difluor-3-butenyl- oder 4,4-difluor-3-halogen-3-butenylester-derivate und ihre verwendung als schädlingsbekämpfungsmittel - Google Patents

4,4-difluor-3-butenyl- oder 4,4-difluor-3-halogen-3-butenylester-derivate und ihre verwendung als schädlingsbekämpfungsmittel

Info

Publication number
EP0846099A1
EP0846099A1 EP96929246A EP96929246A EP0846099A1 EP 0846099 A1 EP0846099 A1 EP 0846099A1 EP 96929246 A EP96929246 A EP 96929246A EP 96929246 A EP96929246 A EP 96929246A EP 0846099 A1 EP0846099 A1 EP 0846099A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
alkoxy
formula
spp
optionally substituted
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP96929246A
Other languages
German (de)
English (en)
French (fr)
Inventor
Udo Kraatz
Wolfram Andersch
Andreas Turberg
Norbert Mencke
Dennis Paul Phillion
Peter Gerrard Ruminski
Gopichand Yalamanchili
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Monsanto Co
Original Assignee
Bayer AG
Monsanto Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE1995131276 external-priority patent/DE19531276A1/de
Application filed by Bayer AG, Monsanto Co filed Critical Bayer AG
Publication of EP0846099A1 publication Critical patent/EP0846099A1/de
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C229/56—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in ortho-position
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • 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
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/20—N-Aryl derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/77—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing carboxyl groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
    • C07C69/88—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with esterified carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof

Definitions

  • the present invention relates to new esters, processes for their preparation and their use for controlling animal pests, in particular of
  • Insects, arachnids and nematodes that are found in agriculture, in the forest, in the protection of stocks and materials, and in the hygiene sector.
  • R 1 represents hydrogen or halogen
  • R 2 represents hydrogen, nitro, cyano, halogen, alkyl, alkoxy, alkylthio or optionally substituted aryl and
  • R 3 represents COOH, SO 3 H, NR 4 R 5 or OR 6 , wherein
  • R 4 represents hydrogen, alkyl or optionally substituted aryl
  • R 5 represents hydrogen, alkyl, optionally substituted aryl or COR 7 ,
  • R 6 represents hydrogen, optionally substituted aralkyl, CONR 4 R 5 or COR 7 ,
  • R represents alkyl, alkenyl, optionally substituted aryl or
  • R 8 represents hydrogen, alkyl or optionally substituted aryl
  • Z is an aliphatic group with one to four carbon atoms, with the proviso that R 9 is not phenyl when Z is CH 2 ,
  • W represents oxygen or sulfur
  • R 9 ⁇ for an aromatic group or for a heterocyclic group (such as a cyclic group from the
  • Cyano trimethylsilyl, hydroxy, alkoxy, halogen, nitro, optionally mono- or disubstituted by alkyl, amino, thiol, alkylthio, phenyl, a residue of a sulfonic acid, phosphonic acid, phosphinic acid or carboxylic acid or an ester, amide or
  • R 12 represents hydrogen or an aliphatic or aromatic group, which is in each case optionally substituted by at least one substituent from the series alkyl having one to four carbon atoms, hydroxy, alkoxy, halogen, nitro, optionally mono- or disubstituted by alkyl Amino, thiol, alkylthio, a residue of a sulfonic acid, Phosphonic acid, phosphinic acid or carboxylic acid or an ester, amide or thioester of one of the acids or phenyl mentioned, then can
  • R 16 and R 17 independently of one another represent hydrogen, alkyl or aryl
  • R 18 represents hydrogen, alkyl, haloalkyl or aryl
  • R 19 and R 20 independently of one another represent hydrogen, alkyl, aryl, alkyl, alkylthio, arylthio, alkylamino, dialkylamino, arylamino or OR 21 and
  • R 21 represents hydrogen, alkyl or aryl
  • R 10 and R 11 independently of one another represent R 22 , OR 22 , SR 22 or NR 22 R 23 , in which
  • R 22 and R 23 independently of one another represent hydrogen or an aliphatic or aromatic group, which are each optionally substituted by at least one substituent from the series cyano, trimethylsilyl, hydroxyl, alkoxy, halogen, nitro, amino which is mono- or disubstituted by alkyl, Thiol, alkylthio, phenyl, a residue of a sulfonic acid, phosphonic acid, phosphinic acid or carboxylic acid or an ester, amide or thioester of one of the acids mentioned
  • the compounds of formula (I) can be present as salts if they are used for
  • Functional groups capable of salt formation include, for example, the carboxyl group and the hydroxyl group.
  • suitable cations are alkali and alkaline earth metal ions such as sodium, calcium, potassium and magnesium, quaternary ammonium ions such as the ammonium ion itself, but also mono-, di- and trialkylammonium ions such as the isopropylammonium ion, and furthermore, for example, the pyridinium ion.
  • group Q Including the meaning of group Q, the following compounds of the formula (Ia), (Ib-1) or (Ib-2) are obtained:
  • CF 2 CR 1 -CH 2 -CH 2 -O-CO-ZR 9 (Ib-1)
  • R 1 , R 2 , R 3 , R 9 , R 10 , R 11 , Z and W have the meaning given above.
  • 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.
  • X ⁇ represents an alkali metal ion or an ammonium ion
  • R 2 and R 3 have the meaning given above
  • R 1 has the meaning given above
  • R 2 , R 3 and R 4 have the meaning given above,
  • Y stands for CO or SO 2
  • the compounds of the formula (Ib) ((Ib-1) or (Ib-2)) can be prepared by generally known methods.
  • the starting compounds required for this can easily be prepared by known methods and / or are commercially available.
  • Pests in particular insects, arachnids and nematodes, which are found in agriculture, in the forests, in the protection of stored goods and materials, and in the hygiene sector.
  • aryl carboxylic acid esters according to the invention are generally defined by the formula (Ia). Preferred substituents or ranges of the radicals listed in the formulas mentioned above and below are explained below:
  • R 1 preferably represents hydrogen, fluorine, chlorine or bromine.
  • R 2 preferably represents hydrogen, nitro, cyano, fluorine, chlorine, bromine, C j -C 8 - alkyl, C] -C6 alkoxy, C 1 -C 6 alkylthio or optionally substituted by cyano,
  • R 3 preferably represents 2-COOH, 2-SO 3 H, NR 4 R 5 or OR 6 .
  • R 4 preferably represents hydrogen, C] -C 8 alkyl or optionally substituted by cyano, fluorine, chlorine, bromine, C j -C 8 alkyl or C ⁇ C 8 -alkoxy-substituted phenyl.
  • R 5 preferably represents hydrogen, C 1 -C 8 -alkyl, phenyl optionally substituted by cyano, fluorine, chlorine, bromine, C 1 -C 6 -alkyl or C 1 -C 6 -alkoxy or COR 7 .
  • R 6 preferably represents hydrogen, optionally substituted by cyano, fluorine, chlorine, bromine, C 1 -C 6 -alkyl or C ] -C 6 -alkoxy-substituted phenyl-C 1 -C 8 -alkyl, for CONR 4 R 5 or COR 7 .
  • R preferably represents C j -CG alkyl, C 2 -C 6 alkenyl, optionally substituted by
  • R 8 preferably represents hydrogen, C r C 8 alkyl or optionally through
  • R 1 particularly preferably represents hydrogen or fluorine.
  • R 2 particularly preferably represents hydrogen, nitro, cyano, fluorine, chlorine, bromine, C r C 4 alkyl, C r C 4 alkoxy, C 1 -C 4 alkylthio or optionally by fluorine, chlorine or C j -C 4 alkoxy substituted phenyl.
  • R 3 particularly preferably represents 2-COOH, 2-SO 3 H, NR 4 R 5 or OR 6 .
  • R 4 particularly preferably represents hydrogen, C j -Q j -alkyl or phenyl optionally substituted by fluorine, chlorine, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy.
  • R5 is particularly preferably hydrogen, C j ⁇ -C alkyl, optionally substituted by fluorine, chlorine, C 1 -C 4 alkyl or C 1 -C 4 -alkoxy-substituted phenyl or COR. 7
  • R 6 particularly preferably represents hydrogen, optionally by fluorine.
  • R 7 particularly preferably represents C j ⁇ -C alkyl, C 2 -C 6 - alkenyl, optionally substituted by fluorine, chlorine or C r C 4 alkyl-substituted phenyl or NR 4 R. 8
  • R 8 particularly preferably represents hydrogen, C j -C 4 - alkyl or optionally substituted by fluorine, chlorine, C j -C 4 alkyl or C j -C 4 -alkoxy-substituted phenyl.
  • a particularly emphasized group of compounds of formula (I) is that in which R 1 is fluorine, R 2 is hydrogen and R 3 is the radical NR 4 R 5 .
  • halogen alone or in combination with other radicals stands for fluorine, chlorine, bromine or iodine.
  • alkyl represents straight-chain or branched groups of one to about seven carbon atoms.
  • lower alkyl stands for a group with one to about four carbon atoms.
  • aliphatic stands for saturated or unsaturated alkyl groups with one to about ten carbon atoms or as indicated or for straight-chain or branched alkenyl groups having two to about ten carbon atoms or as indicated.
  • alkoxy stands for a lower alkyl group which is bonded via oxygen.
  • alkylthio stands for a lower alkyl group which is bonded via sulfur.
  • alkoxycarbonyl stands for a lower alkyl ester of a carboxylic acid.
  • the term "residue of a carboxylic acid, sulfonic acid, phosphinic acid, phosphonic acid or an amide, ester or thioester of one of the acids mentioned” stands for an aliphatic group in which at least one (preferably one) carbon atom is represented by a carboxyl group (COOH), a sulfonic acid group, a phosphinic acid group or a phosphonic acid group is replaced or by a lower alkyl ester, an amide or a lower alkylthioester of one of the acids mentioned.
  • amino acid means any compound that has an amino group and an acid group separated by a carbon atom. This includes natural amino acids, but also those with other substituents on the central carbon atom.
  • alkyl- or arylsulfonamide stands for a sulfonamide group which is substituted by a lower alkyl group or a phenyl group, which in turn may optionally be substituted.
  • heterocyclic stands for any cyclic compound which contains at least one element other than carbon as a ring member.
  • the ring can be saturated or unsaturated.
  • the heteroatom can be oxygen, nitrogen, sulfur or another element.
  • the heterocycles include, for example, radicals of thiadiazole, pyridine, thiazole, isothiazole, oxazole, imidazole, pyrazole, Triazole, benzothiazole, morpholine, piperidine, piperazine and pyrrolidine and can each be substituted by at least one substituent from the group residue of a sulfonic acid, phosphonic acid, phosphinic acid, an ester, amide or thioester of one of these acids, cyano, trimethylsilyl, hydroxy, alkoxy, halogen , Nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl and phenyl.
  • a very particularly preferred compound of formula (Ib) among those mentioned here is N - [(1,1-dimethylethoxy) carbonyl] -L-alanine-3,4,4-trifluoro-3-butenyl ester.
  • preferred among the compounds of the formula (Ia) are the compounds of the formula (Ia) in which there is a combination of the meanings listed above as preferred (preferred).
  • particularly preferred among the compounds of the formula (Ia) are the compounds of the formula (Ia) in which there is a combination of the meanings listed above as being particularly preferred.
  • hydrocarbon radicals such as alkyl or alkenyl
  • heteroatoms such as
  • Alkoxy or alkylthio - as far as possible, straight-chain or branched.
  • Process A) described above for the preparation of compounds of the formula (Ia) is characterized in that benzoic acid derivatives of the formula (II) with fluorobutenyl bromides of the formula (III) in the presence of a diluent.
  • Suitable diluents are, in particular, organic solvents, for example optionally chlorinated aromatic hydrocarbons such as toluene, xylene or chlorobenzene, ethers such as dioxane or tetrahydrofuran, nitriles such as
  • Acetonitrile such as dimethyl sulfoxide, amides such as dimethylformamide or carboxylic acid esters such as ethyl acetate.
  • the reaction temperature can be varied within a wide range in process A). In general, temperatures between 0 ° C and 160 ° C, preferably between 20 ° C and 120 ° C.
  • the molar ratio of the compound of formula (II) to the compound of formula (III) is generally 2: 1 to 1: 2.
  • the reaction is generally carried out under normal pressure.
  • reaction mixture is hydrolyzed, for example, the product with an organic solvent such as ethyl acetate, dichloromethane or
  • Process B) described above for the preparation of compounds of the formula (Ia) is characterized in that isatoic anhydrides of the formula (IV) are reacted with fluorobutenols of the formula (V), if appropriate in the presence of a diluent and if appropriate in the presence of a base .
  • Halogenated aliphatic or aromatic hydrocarbons such as cyclohexane, toluene, xylene, dichloromethane, chloroform, dichloroethane or chlorobenzene or ethers such as tetrahydrofuran or
  • the reaction can also be carried out in the absence of one of the solvents mentioned. In this case, it may be advantageous to use the fluorobutenol of the formula (V) in excess.
  • Amines preferably tertiary amines such as triethylamine, pyridine or diazabicycloundecene (DBU) or inorganic bases, e.g. Alkali metal carbonates, hydrogen carbonates or hydroxides such as potassium carbonate, sodium hydrogen carbonate or sodium hydroxide.
  • tertiary amines such as triethylamine, pyridine or diazabicycloundecene (DBU)
  • inorganic bases e.g. Alkali metal carbonates, hydrogen carbonates or hydroxides such as potassium carbonate, sodium hydrogen carbonate or sodium hydroxide.
  • reaction temperature can be varied over a wide range. In general, temperatures from 0 ° C to 180 ° C, preferably from 20 ° C to 140 ° C.
  • the compounds of the formulas (IV) and (V) are generally used in a molar ratio of 1: 2 to 2: 1.
  • the reaction is generally carried out under normal pressure.
  • the reaction mixture is hydrolyzed, the product is extracted with an organic solvent such as ethyl acetate, dichloromethane or toluene, and the solvent is then removed.
  • organic solvent such as ethyl acetate, dichloromethane or toluene
  • Formula (Ia) is characterized in that acid anhydrides of the formula (VI) are reacted with a fluorobutenol of the formula (V), if appropriate in the presence of a diluent and if appropriate in the presence of a base.
  • the benzoic acid derivatives of the formula (II) required as starting materials in production process A) can be obtained in a simple, known manner by reaction of the corresponding benzoic acids (which are easy to prepare and the largest Some are commercially available) with bases (for example alkali metal hydroxides such as lithium hydroxide, potassium hydroxide or sodium hydroxide or amines such as dimethylamine, triethylamine or butylamine).
  • bases for example alkali metal hydroxides such as lithium hydroxide, potassium hydroxide or sodium hydroxide or amines such as dimethylamine, triethylamine or butylamine.
  • the isatoic anhydrides of the formula (IV) required as starting materials in production process B) are known and / or can be prepared by known methods (Methods of Organ. Chemistry - Houben-Weyl, Vol. 4E, p. 214 ff (1983 )).
  • the acid anhydrides of formula (VI) required as starting materials in production process C) are known and / or can be prepared by known methods (Methodicum Chimicum, C-Oharmen, Vol. 5, p. 614 ff. (1975)).
  • the active substances are suitable for controlling animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species and against all or individual stages of development.
  • the pests mentioned above include:
  • Thysanura for example Lepisma saccharina.
  • Collembola for example Onychiurus armatus.
  • Orthoptera e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
  • Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.
  • Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis,
  • Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis,
  • Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
  • Drosophila melanogaster Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tabanus spp.
  • Tannia spp. Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.
  • Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp., Ctenocephalides felis.
  • Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp.,
  • Rhipicephalus spp. Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..
  • Plant-parasitic nematodes include, for example, Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp ..
  • the compounds of the formula (I) according to the invention are notable in particular for an outstanding nematicidal action, for example against Meloidogyne incognita.
  • the active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances as well as very fine encapsulations in polymers
  • formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can also be used as auxiliary solvents.
  • auxiliary solvents e.g. organic solvents
  • aromatics such as xylene, toluene, or alkylnaphthalenes
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
  • aliphatic hydrocarbons such as cyclohexane or paraffins, e.g.
  • Petroleum fractions mineral and vegetable oils, 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
  • Possible solid carriers are: e.g. Ammonium salts and natural rock flours, such as kaolins, clays,
  • Talc chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic stone powder, such as highly disperse silica, aluminum oxide and
  • Silicates are suitable as solid carriers for granules: eg broken ones and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks;
  • suitable emulsifying 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 dispersants are: eg 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% by weight of active compound, preferably between 0.5 and 90%.
  • the active substance according to the invention can be present in its commercially available formulations and in the use forms prepared from these formulations in a mixture with other active substances, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
  • Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.
  • copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxyne copper and Bordeaux mixture, Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazole, Methasulfocarb, Methfuroxam, Metir , Metsulfovax, Myclobutanil, Nickel-dimethyldithiocarbamate, Nitrothal-isopropyl, Nuarimol, Ofurace, Oxadixyl, Oxamocarb, Oxycarboxin,
  • PCNB Quintozen
  • Tebuconazole Tebuconazole, tecloftalam, tecnazen, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, trichlamide, tricyclazole, tridemorph, triflorizolinol, triflorizolinol, valid , Zineb, ziram.
  • Fenamiphos Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenproothat, Fufionfox, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufone HCH, heptenophos, hexaflumuron, hexythiazox,
  • Imidacloprid Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Iver ⁇ mectin, Lambda-cyhalothrin, Lufenuron, Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos,
  • Methamidophos Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin, Naled, NC 184, NI 25, Nitenpyram, Omethoat, Oxamyl, Oxydemethon M, Oxydeprofos, Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophhine, Pyrachlophhion, Pyrachlophion, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlop
  • the active compounds according to the invention can also be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists.
  • Synergists are compounds through which the action of the active ingredients is increased without the added synergist itself having to be active.
  • the active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges.
  • the active substance concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, preferably between 0.0001 and 1% by weight.
  • the application takes place in a customary manner adapted to the application forms.
  • the active ingredient When used against hygiene and storage pests, the active ingredient is characterized by an excellent residual effect on wood and clay as well as a good stability to alkali on limed substrates.
  • the active compounds according to the invention act not only against plant, hygiene and stored-product pests, but also in the veterinary sector against animal parasites (ectoparasites) such as tick ticks, leather ticks, and mite mites, Running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, featherlings and fleas.
  • animal parasites ectoparasites
  • tick ticks such as tick ticks, leather ticks, and mite mites, Running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, featherlings and fleas.
  • Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp ..
  • Ischnocerina e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp ..
  • Nematocerina and Brachycerina e.g. Aedes spp., Anopheles spp., Culex spp., Simulium spp.
  • Siphonaptrida e.g. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp ..
  • Hyalomma spp. Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneu- monyssus spp., Sternostoma spp., Varroa spp ..
  • Actinedida Prostigmata
  • Acaridida Acaridida
  • Acarapis spp. Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp. , Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp ..
  • the active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which are used in agricultural animals, such as e.g. Cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as e.g. Dogs, cats, house birds, aquarium fish and so-called experimental animals such as Infest hamsters, guinea pigs, rats and mice.
  • arthropods By combating these arthropods, deaths and reduced performance (in the case of meat, milk, wool, skins, eggs, honey, etc.) are to be reduced, so that the use of the active compounds according to the invention enables more economical and simple animal husbandry.
  • the active compounds according to the invention are used in the veterinary sector 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 Example by injections (intramuscular, subcutaneous, intravenous, intraperitonal, 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 aid of shaped articles containing active ingredients, such as collars, ear tags, tail tags, limb tapes, holsters, marking devices, etc.
  • enteral administration in the form of, for example, tablets, capsules, drinkers, drenches, granules, pastes, boluses, the feed-through method, suppositories
  • parenteral administration such as
  • the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, flowable agents) which contain the active compounds in an amount of 1 to 80% by weight, directly or apply after 100 to 10,000-fold dilution or use it as a chemical bath.
  • formulations for example powders, emulsions, flowable agents
  • Test nematode Meloidogyne incognita solvent: 4 parts by weight acetone
  • 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, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
  • the active ingredient preparation is mixed intimately with soil that is heavily contaminated with the test nematodes.
  • the treated soil is filled into pots, lettuce is sown and the pots are kept at a greenhouse temperature of 25 ° C.
  • the lettuce roots are examined for nematode infestation (root galls) and the effectiveness of the active ingredient is determined in%.
  • the degree of efficiency is 100% if the infestation is completely avoided, it is 0% if the infestation is exactly as high as that of the control plants in untreated but contaminated soil in the same way.
  • Test animals All larval stages of Lucilia cuprina (OP-resistant)
  • Emulsifier 35 parts by weight of nonylphenol polyglycol ether
  • 30 to 50 larvae per concentration are placed on horse meat (1 cm 3 ) in glass tubes, onto which 500 ⁇ l of the dilution to be tested are pipetted.
  • the glass tubes are placed in plastic beakers, the bottom of which is covered with sea sand, and stored in an air-conditioned room (26 ° C ⁇ 1.5 ° C, 70% relative humidity ⁇ 10%). The effects are checked after 24 hours and 48 hours (larvicidal action). After the larvae have emigrated (approx. 72 h), the glass tubes are removed and perforated plastic lids are placed on the beakers. After l' ⁇ times the development period (hatching of the control flies), the hatched flies and the dolls / doll covers are counted.
  • Larvae after 48 h (larvicidal effect), or the inhibition of adult hatching from the pupa or the inhibition of pupa formation.
  • the criterion for the in vitro effect of a substance is the inhibition of flea development or a development standstill before the adult stage. 100% larvicidal activity means that all larvae have died after 48 hours. 100% development inhibitory effect means that no adult flies have hatched.
  • Test animals Adult suckled females
  • the test is carried out in 5-fold determination. 1 ⁇ l of the solutions is injected into the abdomen, the animals are transferred to dishes and stored in an air-conditioned room. The effect is determined by the inhibition of egg laying. 100% means that no tick has laid.
  • the compounds according to Preparation Examples 1 and 5 showed an activity of 100% at an exemplary active ingredient concentration of 20 ⁇ g / animal.
  • the compound according to preparation example 26 had an activity of 95% at 500 ppm in method 1, at one

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Wood Science & Technology (AREA)
  • Agronomy & Crop Science (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Zoology (AREA)
  • Molecular Biology (AREA)
  • Biochemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Medicinal Preparation (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
EP96929246A 1995-08-25 1996-08-13 4,4-difluor-3-butenyl- oder 4,4-difluor-3-halogen-3-butenylester-derivate und ihre verwendung als schädlingsbekämpfungsmittel Ceased EP0846099A1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US327995P 1995-08-25 1995-08-25
US3279P 1995-08-25
DE1995131276 DE19531276A1 (de) 1995-08-25 1995-08-25 Arylester
DE19531276 1995-08-25
PCT/EP1996/003569 WO1997008130A1 (de) 1995-08-25 1996-08-13 4,4-difluor-3-butenyl- oder 4,4-difluor-3-halogen-3-butenylester-derivate und ihre verwendung als schädlingsbekämpfungsmittel

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Publication Number Publication Date
EP0846099A1 true EP0846099A1 (de) 1998-06-10

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EP96929246A Ceased EP0846099A1 (de) 1995-08-25 1996-08-13 4,4-difluor-3-butenyl- oder 4,4-difluor-3-halogen-3-butenylester-derivate und ihre verwendung als schädlingsbekämpfungsmittel

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EP (1) EP0846099A1 (zh)
JP (1) JPH11510474A (zh)
KR (1) KR19990044035A (zh)
CN (1) CN1200108A (zh)
AU (1) AU6872896A (zh)
BR (1) BR9610022A (zh)
CA (1) CA2230031A1 (zh)
TR (1) TR199800296T1 (zh)
WO (1) WO1997008130A1 (zh)

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DE19922934A1 (de) * 1999-05-19 2000-11-23 Bayer Ag Neue Halogenverbindungen
AU2160201A (en) * 1999-11-19 2001-05-30 Novartis Ag Organic compounds and their use in the control of ectoparasites
DE60228111D1 (de) * 2001-09-28 2008-09-18 Kumiai Chemical Industry Co Difluoralkenderivat, dieses enthaltende mittel zur bekämpfung von schädlingen und zwischenprodukt dafür
WO2003042153A1 (fr) * 2001-11-15 2003-05-22 Kumiai Chemical Industry Co., Ltd. Derive de difluoroalcene, et pesticide renfermant ce derive
AU2003252536A1 (en) * 2002-08-01 2004-02-23 Basf Aktiengesellschaft Pesticidal fluoroalkene derivatives
CN105377034A (zh) * 2013-07-18 2016-03-02 Fmc有限公司 线虫驱除组合物
IT201900001339A1 (it) * 2019-01-30 2020-07-30 Isagro Spa Derivati teofillinici ad attività nematocida, loro composizioni agronomiche e relativo uso
CN113912495A (zh) * 2020-07-09 2022-01-11 山东省联合农药工业有限公司 一种含氟丁烯酯类衍生物及其制备方法与用途
TW202229241A (zh) 2020-09-26 2022-08-01 印度商皮埃企業有限公司 殺線蟲化合物及其用途

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US4952580A (en) * 1985-06-20 1990-08-28 Fmc Corporation Pesticidal polyhaloalkene derivatives
US4950666A (en) * 1989-03-30 1990-08-21 Fmc Corporation Difluoroalkane and difluoroalkenylalkane pesticides
DE3941966A1 (de) * 1989-12-15 1991-06-20 Schering Ag Halogenierte olefine, verfahren zu ihrer herstellung und ihre verwendung als schaedlingsbekaempfungsmittel
DE4445792A1 (de) * 1994-12-21 1996-06-27 Bayer Ag Fluorbutenyl(thio)ether

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Title
See references of WO9708130A1 *

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TR199800296T1 (xx) 1998-06-22
BR9610022A (pt) 1999-07-06
WO1997008130A1 (de) 1997-03-06
JPH11510474A (ja) 1999-09-14
KR19990044035A (ko) 1999-06-25
AU6872896A (en) 1997-03-19
CN1200108A (zh) 1998-11-25
CA2230031A1 (en) 1997-03-06

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