EP0741698A1 - Derives d'acide phenylthio acetique, leur procede de preparation, produits intermediaires utilises a cet effet, et agents les contenant - Google Patents

Derives d'acide phenylthio acetique, leur procede de preparation, produits intermediaires utilises a cet effet, et agents les contenant

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Publication number
EP0741698A1
EP0741698A1 EP95906289A EP95906289A EP0741698A1 EP 0741698 A1 EP0741698 A1 EP 0741698A1 EP 95906289 A EP95906289 A EP 95906289A EP 95906289 A EP95906289 A EP 95906289A EP 0741698 A1 EP0741698 A1 EP 0741698A1
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EP
European Patent Office
Prior art keywords
alkylamino
alkyl
aryl
halogen
hetaryl
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.)
Withdrawn
Application number
EP95906289A
Other languages
German (de)
English (en)
Inventor
Herbert Bayer
Hubert Sauter
Ruth Müller
Wassilios Grammenos
Albrecht Harreus
Reinhard Kirstgen
Franz Röhl
Eberhard Ammermann
Gisela Lorenz
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.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0741698A1 publication Critical patent/EP0741698A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • A01N37/50—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 the nitrogen atom being doubly bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/20—Esters of monothiocarboxylic acids
    • C07C327/22—Esters of monothiocarboxylic acids having carbon atoms of esterified thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms

Definitions

  • the present invention relates to phenylacetic acid derivatives of the formula I.
  • R 1 is hydrogen and -CC alkyl
  • n 0, 1 or 2, where the radicals R 2 can be different if represents 2;
  • R 3 is hydrogen, cyano, nitro, hydroxy, amino, halogen,
  • R 4 is hydrogen, cyano, nitro, hydroxy, amino, halogen,
  • N-C ⁇ -C 6 -alkylamino where the hydrocarbon radicals of these groups can be partially or completely halogenated or can carry one to three of the following radicals: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, amino hiocarbonyl, halogen, C ⁇ -C 6 alkylaminocarbonyl,
  • A represents oxygen, sulfur or nitrogen and the nitrogen carries hydrogen or Ci-C ⁇ -alkyl
  • n 0 or 1
  • R 6 is hydrogen or Ci-Ce-alkyl
  • R 7 is hydrogen or -CC 6 alkyl, as well as their salts.
  • the invention also relates to processes and intermediates for the preparation of these compounds and compositions containing them for controlling animal pests and harmful fungi.
  • Phenylacetic acid derivatives for pest control are known from the literature (EP-A 432 503, EP-A 463 488).
  • the present invention was based on new compounds with improved activity as an object.
  • the compounds I can be obtained in various ways by processes known per se in the literature.
  • the structure of the grouping -C (NOCH 3 ) -COSR 1 is known, for example, from the literature cited at the beginning.
  • L 1 in formula II stands for a nucleophilically exchangeable leaving group, for example halogen or sulfonate groups, preferably chlorine, bromine, iodine, mesylate, tosylate or triflate.
  • the reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base, e.g. Sodium hydride, potassium hydroxide, potassium carbonate and triethylamine according to the methods described in Houben-Weyl, vol. E 14b, p. 370 f and Houben-Weyl, vol. 10/1, p. 1189 f.
  • a base e.g. Sodium hydride, potassium hydroxide, potassium carbonate and triethylamine according to the methods described in Houben-Weyl, vol. E 14b, p. 370 f and Houben-Weyl, vol. 10/1, p. 1189 f.
  • the required hydroxyimine III is obtained by reacting a corresponding dihydroxyimine IV with a nucleophilically substituted reagent VI
  • L 2 in formula VI stands for a nucleophilically exchangeable leaving group, for example halogen or sulfonate groups, preferably chlorine, bromine, iodine, mesylate, tosylate or triflate.
  • reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base, e.g. Potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine according to the in Houben-Weyl, Vol. E 14b,
  • a base e.g. Potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine according to the in Houben-Weyl, Vol. E 14b,
  • the compounds I can also be obtained by first reacting the benzyl derivative II with the dihydroxyimino derivative IV into a corresponding benzyloxime of the formula V, V then being converted to I with the nucleophilically substituted reagent VI.
  • the reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base, e.g. Potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine according to the in Houben-Weyl, Vol. 10/1, p. 1189 f; Houben-Weyl, Vol. E 14b, p. 307 f, p. 370 f and p. 385 f; Houben-Weyl, Vol. 10/4, p. 55 f, p. 180 f and p. 217 f; Houben-Weyl, vol. E5, p. 780 f.
  • a base e.g. Potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine according to the in Houben-Weyl, Vol. 10/1, p. 1189 f; Houben-Weyl, Vol. E 14b, p. 307 f,
  • Q ⁇ in formula IXb stands for the anion of an acid, in particular an inorganic acid, e.g. Halide such as chloride.
  • reaction is carried out in a manner known per se in an inert organic solvent according to that described in EP-A 513 580; Houben-Weyl, Vol. 10/4, pp. 73 f; Houben-Weyl, Vol. E14b, p. 369 f and p. 385 f.
  • the compounds I can also be obtained by first reacting the benzyl derivative II with the carbonylhydroxyimino derivative VIIa into a corresponding benzyloxyimine of the formula VIII, VIII subsequently being converted to I with the hydroxylamine IXa or its salt IXb.
  • the reaction is carried out in a manner known per se in an inert organic solvent according to that in Houben-Weyl, vol. E14b, p. 369 f; Houben-Weyl, vol. 10/1, p. 1189 f and Hou ⁇ ben-Weyl, vol. 10/4, p. 73 f or EP-A 513 580.
  • reaction is carried out in a manner known per se in an inert orange solvent in accordance with the methods described in EP-A 463 488 and DE application. No. 42 28 867.3 methods described.
  • the required carbonyl compound X is obtained e.g. by reacting a corresponding hydroxyiminocarbonyl Vllb with a nucleophilically substituted reagent VI
  • the compounds I can also be obtained by first reacting the benzylhydroxylamine Ha with the hydroxyiminocarbonyl Vllb in the corresponding benzyloxyimine of the formula V, V then being converted to I with the nucleophilically substituted reagent VI as described above .
  • the compounds I can also be prepared by first converting the benzylhydroxylamine Ha with the dicarbonyl of the formula XI into the benzyloxyimine of the formula VIII and then VIII with the hydroxylamine IXa or its salt IXb as described above for I is implemented.
  • R 3 is not halogen
  • Compounds in which R 3 is not halogen are preferably obtained by first converting a compound X according to the methods described in EP-A 493 711 with a lactone XII into the corresponding benzoic acid XIII and XIII via the corresponding ones Halides are converted into the cyanocarboxylic acids XIV, which are then converted into the ⁇ -keto esters XV by the Pinner reaction (Angew. Chem. 94, 1 (1982)). The corresponding thioesters are obtained from the derivatives XV by "transesterification" and are subsequently converted into the compounds I.
  • the compounds II can according to the in EP-A 432 503,
  • the compounds I can be produced as E / Z isomer mixtures which, for example, can be separated into the individual compounds by crystallization or chromatography in the usual way.
  • isomer mixtures occur during the synthesis, however, a separation is generally not absolutely necessary since the individual isomers can partially convert into one another during preparation for use or during use (e.g. under the influence of light, acid or base). Corresponding conversions can also take place after use, for example in the treatment of plants in the treated plant or in the harmful fungus or animal pest to be controlled.
  • the E isomers of the compounds I are preferred in terms of their activity (configuration based on the -0CH 3 group in relation to the -COSR 1 group).
  • the cis isomers of the compounds I are preferred in terms of their activity (configuration based on the radical R 3 in relation to the -OCH group).
  • Alkyl straight or branched alkyl groups with 1 to 4, 6 or 10 carbon atoms, e.g. Ci-C ⁇ -alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1, 2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl
  • Alkylcarbonyl straight-chain or branched alkyl groups with 1 to 10 carbon atoms, which are bonded to the skeleton via a carbonyl group (-CO-);
  • Alkylaminothiocarbonyl Alkylamino groups with 1 to 6 carbon atoms as mentioned above, which are bonded to the skeleton via a thiocarbonyl group (-CS-);
  • Dialkylamino groups each having 1 to 6 carbon atoms per alkyl radical as mentioned above, which are bonded to the skeleton via a thiocarbonyl group (-CS-);
  • Halo ⁇ enalkyl straight-chain or branched alkyl groups with 1 to 6 carbon atoms, in which groups the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms as mentioned above, for example C 1 -C 2 -haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, Difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2- difluoro-ethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;
  • Haloalkoxy straight-chain or branched alkyl groups with 1 to 6 carbon atoms, the hydrogen atoms in these groups being partially or completely replaced by halogen atoms as above hend called may be replaced, and wherein these groups are bonded to the structure via an oxygen atom;
  • Alkylthio straight-chain or branched alkyl groups with 1 to 4 or 6 carbon atoms as mentioned above, which are bonded to the skeleton via a sulfur atom (-S-), for example C 1 -C 6 -alkyl thio such as methylthio, ethylthio, propylthio, 1-methylethylthio, Butylthio, 1-methylpropylthio, 2-methylpropylthio, 1,1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1,1- Dimethylpropylthio, 1,2-Dirnethylpropylthio, 1-Methylpentylthio, 2-Methylpentylthio, 3-Methylpentylthio,
  • Cvcloalkyl monocyclic alkyl groups with 3 to 6 carbon ring members, e.g. Cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
  • Alk ⁇ nyloxy straight-chain or branched alkenyl groups with 2 to 6 carbon atoms and a double bond in any position, which are bonded to the skeleton via an oxygen atom (-0-);
  • Alk ⁇ nylcarbonyl straight-chain or branched alkenyl groups with 2 to 10 carbon atoms and a double bond in any position which are bonded to the skeleton via a carbonyl group (-CO-);
  • Alkenvlthio or Alkenvlamino straight-chain or branched alkenyl groups with 2 to 6 carbon atoms and a double bond in any position which (alkenylthio) are bonded to the skeleton via a sulfur atom or (alkenylamino) a nitrogen atom;
  • Alkynyl straight-chain or branched alkynyl groups with 2 to 10 carbon atoms and a triple bond in any position, for example C -C 6 -alkynyl such as ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl , 3-pentynyl, 4-pentynyl, l-methyl-2-butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 1, l-dimethyl-2-propynyl, l-ethyl-2-propynyl , 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, l-methyl-2-pentynyl, l-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-p
  • Alkynylcarbonyl straight-chain or branched alkynyl groups with 3 to 10 carbon atoms and a triple bond in any position, which are bonded to the skeleton via a carbonyl group (-CO-);
  • Alkinvloxv or Alkinvlthio and Alkinvlamino straight-chain or branched alkynyl groups with 2 to 6 carbon atoms and a triple bond in any position, which (alkynyloxy) via an acid atom or (alkynylthio) via a sulfur atom or (alkynylamino) via a nitrogen atom are bonded to the skeleton; Pvcloalkoxy or Cycloalkylthio and Cvcloalkyl «minn; monocyclic alkenyl groups with 3 to 6 carbon ring members which (cycloalkyloxy) are bonded to the skeleton via an oxygen atom or (cycloalkylthio) a sulfur atom or (cycloalkylamino) via a nitrogen atom, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl ;
  • Cvcloalkanvl or Cvcloalkenvloxy Cycloalkenylthio and Cvclo- monocyclic alkenyl groups with 3 to 6 carbon ring members, which directly or (cycloalkenyloxy) via one
  • Oxygen atom or (cycloalkenylthio) a sulfur atom or (cycloalkenylamino) are bonded to the skeleton via a nitrogen atom, e.g. Cyclopropenyl, cyclobutenyl, cyclopentenyl or cyclohexenyl;
  • Aromatic mono- or polycyclic hydrocarbon residues which are bonded to the skeleton via a nitrogen atom;
  • Hetarylcarbonyl and hetarylaulfonyl aromatic mono- or polycyclic radicals which, in addition to carbon ring members, can additionally contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom or one oxygen or one sulfur atom and which or (hetaryloxy ) via an oxygen atom (-0-) or (hetarylthio) a sulfur atom (-S-), (hetarylcarbonyl) via a carbonyl group (-C0-) or (hetaryl-sulfonyl) via a sulfonyl group (-S0 2 -) to the skeleton are bound, e.g.
  • 5- ⁇ liedri ⁇ es heteroarvl. containing one to three nitrogen atoms 5-ring heteroaryl groups which, in addition to carbon atoms, can contain one to three nitrogen atoms as ring members, for example 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2- Imidazolyl, 4-imidazolyl, 1,2,4-triazol-3-yl and 1,3,4-triazol-2-yl;
  • heteroarvl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom or one oxygen or one
  • Sulfur atom 5-ring heteroaryl groups which, in addition to carbon atoms, can contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom or one oxygen or sulfur atom as ring members, e.g. 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3- Pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-0xazolyl, 4-0xazolyl, 5-0xazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4- Oxadiazol-3-yl, l, 2,4-oxadiazol-5-yl, 1,2,4-thiadiazol -3-y
  • 6-membered heteroaryl containing one to three or one to four nitrogen atoms 6-ring heteroaryl groups which, in addition to carbon atoms, may contain one to three or one to four nitrogen atoms as ring members, e.g. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, l, 3,5-triazin-2-yl, 1, 2,4-triazin-3-yl and 1,2,4,5-tetrazinyl;
  • Buta-1,3-diene-1,4-diyl group may be bridged, e.g. Quinoline, isoquinoline, quinazoline and quinoxaline,
  • Hetarylffi ⁇ 'iiin '? I aromatic mono- or polycyclic radicals which, in addition to carbon ring members, can additionally contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom or one oxygen or one sulfur atom, and which have one Nitrogen atom are bound to the scaffold.
  • R 3 represents hydrogen, hydroxyl, cyclopropyl, chlorine, methyl, ethyl, 1-methylethyl, methoxy, methylthio or phenyl.
  • R 4 represents hydrogen, hydroxyl, cyclopropyl, chlorine, methyl, ethyl, isopropyl, methoxy or methylthio.
  • R 4 represents aryl or hetaryl.
  • R 5 represents arylalkyl or hetarylalkyl.
  • R 5 represents aryloxyalkyl or hetaryloxyalkyl.
  • R 4 for optionally subst. Aryl or hetaryl is.
  • R 4 for optionally subst.
  • R 4 for optionally subst. Furyl, thienyl or pyrrolyl.
  • R 4 for optionally subst.
  • R 4 for optionally subst. Oxdiazolyl, thiadiazolyl or triazolyl.
  • R 4 is phenyl which is unsubstituted or carries one or two of the following groups: nitro, cyano, hydroxy, amino, aminocarbonyl, aminothiocarbonyl, halogen, C 1 -C 4 alkyl, C 1 -C -Halogenalkyl, C ⁇ -C -alkoxy, C ⁇ -C -halalkalkoxy, C ⁇ -C -alkylamino, di-C 1 -C 4 -alkylamino, C 1 -C 4 -alkylsulfonyl, C ⁇ -C -alkoxycarbonyl, C ⁇ -C 4 -Alkylaminocarbonyl or Di-C ⁇ -C 4 -Alkylaminocarbonyl.
  • R 5 represents aryl or hetaryl.
  • the compounds I are suitable as fungicides.
  • the compounds I are notable for excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes and Basidio ycetes. Some of them are systemically effective and can be used as foliar and soil fungicides.
  • Erysiphe graminis in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants, Podosphaera leucotricha on apples, Uncinula necator on vines, Puc- cinia species on cereals Species on cotton and grass, Ustilago species on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helminthosporium species on cereals, Seporia nodoru on wheat, Botrytis cinerea (gray mold) on strawberries, vines , Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat, barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Fusa7rium and Verticillium species on various plants, Plasmopara viticola on vine
  • the compounds I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally active amount of the active compounds. It is used before or after the infection of the materials, plants or seeds by the fungi.
  • the formulations can be converted into the usual formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the form of application depends on the respective purpose; in any case, it should ensure a fine and uniform distribution of the ortho-substituted benzyl ester of a cyclopropanecarboxylic acid.
  • the formulations are prepared in a known manner, for example by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, and in the case of water as diluent other organic solvents can also be used as auxiliary solvents - nen.
  • auxiliaries solvents such as aromatics (e.g.
  • chlorinated aromatics e.g. chlorobenzenes
  • paraffins e.g. petroleum fractions
  • alcohols e.g. methanol, butanol
  • ketones e.g. cyclohexanone
  • amines e.g.
  • Carriers such as natural stone powder (eg kaolins, clays, talc, chalk) and synthetic stone powder (eg highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste liquors and methyl cellulose.
  • Carriers such as natural stone powder (eg kaolins, clays, talc, chalk) and synthetic stone powder (eg highly disperse silica, silicates)
  • Emulsifiers such as nonionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste liquors and methyl cellulose.
  • the fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active ingredient.
  • the application rates are between 0.01 and 2.0 kg of active ingredient per ha.
  • active ingredient 0.001 to 0.1 g, preferably 0.01 to 0.05 g, per kg of seed are generally required.
  • agents according to the invention can also be present in the use form as fungicides together with other active ingredients, which e.g. with herbicides, insecticides, growth regulators, fungicides or also with fertilizers.
  • Sulfur, dithiocarbamates and their derivatives such as ferridi ethyl dithiocarbamate, zinc dimethyl dithiocarbamate, zinc ethylene bisdithiocarbamate, manganese ethylene bisdithiocarbamate, manganese-zinc ethylene diamine bis-dithiocarbamate, tetra ethyl thiuram disulfide zinc (ammonium n-bisulfide, ethylenedisulfide, (ammonia -dithiocarbamate), ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate), zinc (N, N'-propylene-bis-dithiocarbamate), N, N'-polypropylene-bis- ( thiocarbamoyD disulfide; Nitroderivatives such as dinitro- (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4, 6-dini
  • heterocyclic substances such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, 0.0-diethyl-phthalimidophosphonothioate, 5-amino-l- [bis - (dimethylamino) phosphinyl] -3-phenyl-l, 2,4-triazole, 2,3-dicyano-l, 4-dithioanthraquinone, 2-thio-l, 3-dithiolo [4,5-b] quinoxaline, 1- (butylcarbamoy1) -2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benzimidazole, 2- (furyl- (2)) -benzimidazole, 2- (thiazolyl- (4)) -benzimidazole, N- (1,1,2,2-tetrachloroethyl
  • the compounds of the formula I are also suitable for effectively controlling pests from the class of the insects, arachnids and nematodes. They can be used as pesticides in crop protection and in the hygiene, stored product protection and veterinary sectors.
  • the harmful insects include, for example, Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulobura, chumumobella, Cheumatobella - ferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia po- monella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandio- sella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia am- biguella, Evetria bouliana, Fella diella, granella Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis
  • Diptera From the order of the two-winged species (Diptera), for example, Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropuce phumacuceaculaceacucia, pita Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis, Glos ⁇ sina morsitans, Haematobia irritans, Haplodiplosis equestris, Hy- lemyia platura, Hypoderma lineata, Lirio yza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia seriaalalisata, Lucilia seriola rata,
  • Thysanoptera From the order of the thrips (Thysanoptera), for example, Franklini fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips tabaci.
  • hymenoptera From the order of the hymenoptera (Hymenoptera), for example, Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta.
  • Heteroptera From the order of the bugs (Heteroptera), for example, Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Eu- schistus impictiventris, Leptoglossus phyllopus, Lygus lineola- ris, Lygus parsatidis, Lygus parsatidis, Lygus prairisensis , Solubea insularis, Thyanta perditor.
  • suckers from the order of the plant suckers (Ho optera), for example, Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci, Brachycaudus cardui, Bre- vicoryne brassicae, Cerosipha gossypyususiusi, Dreiafusiai, Dreiafusolia, Dreiafusiaia, Dreiafusiaia, Dreiafusiaia, Dreiafusiaia, Dreyfusiaia, Dreiafusiaia , Empoasca fabae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, Myzodes persicae, Myzus
  • Orthoptera From the order of the straight-winged wing (Orthoptera), for example Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanusus, Melanoplus sanguinisusptipisipei, Melanoplasci, melanoplasmic , Periplaneta americana, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus, Tachycines asynamorus.
  • Orthoptera for example Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus fe
  • arachnids such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus micro-croplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentoretronichumum, Eri Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus mou- bata, Otobius megnini, Paratetranychus pilosus, Dermanyssus gal- linae, Phyllocoptruta oleivora, Polyphagotarsonemususus, Ticendiphodinusiabi, Ticipinusiabi, Ticipinusiabusi, Ticinociabusi - wai, Tetranychus pacificus, Tetranychus
  • root gall nematodes e.g. Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, cyst-forming nematodes, e.g. Globodera rostochiensis, Heterodera avenae, Heterodera glycines, Heterodera schach- tii, Heterodera trifolii, stick and leaf wholes, e.g.
  • root gall nematodes e.g. Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, cyst-forming nematodes, e.g. Globodera rostochiensis, Heterodera avenae, Heterodera glycines, Heterodera schach- tii, Heterodera trifolii, stick and leaf wholes, e.g.
  • the active ingredients as such in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, spreading agents, granules by spraying, atomizing, dusting, scattering or pouring.
  • the application forms depend entirely on the intended use; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • the active substance concentrations in the ready-to-use preparations can be varied over a wide range.
  • they are between 0.0001 and 10%, preferably between 0.01 and 1%.
  • the active ingredients can also be used with great success in the ultra-low-volume process (ULV), it being possible to apply formulations with more than 95% by weight of active ingredient or even the active ingredient without additives.
  • UUV ultra-low-volume process
  • the amount of active ingredient used to control pests is 0.1 to 2.0, preferably 0.2 to 1.0 kg / ha under field conditions.
  • mineral oil fractions from medium to high boiling points such as kerosene or diesel oil, also coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example benzene, toluene, xylene, Paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, Butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents, for example dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, into consideration.
  • solvents for example dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, into consideration.
  • Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water.
  • emulsion concentrates pastes or wettable powders (wettable powders, oil dispersions)
  • wettable powders oil dispersions
  • water water
  • emulsions, pastes or oil dispersions the substances as such or dissolved in an oil or solvent, by means of wetting, adhesive,
  • Dispersants or emulsifiers can be homogenized in water. However, it is also possible to prepare concentrates composed of an active substance, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or oil, which are suitable for dilution with water.
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • the formulations generally contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight, of the active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum). Examples of formulations are:
  • V. 80 parts by weight of an active ingredient are mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 10 parts by weight of the sodium salt of a lignin sulfonic acid from a sulfite waste liquor and 7 parts by weight in powder form Mix the silica gel well and grind it in a hammer mill (active ingredient content 80% by weight).
  • Parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil consists. By pouring and Distributing the solution in 100,000 parts by weight of water gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.
  • Granules e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers.
  • Solid carriers are e.g. Mineral soils, such as silica gel, silicas, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as e.g. Ammonium sulfate,
  • Ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.
  • Oils of various types, herbicides, fungicides, other pesticides, bactericides can be added to the active compounds, if appropriate also only immediately before use (tank mix). These agents can be added to the agents according to the invention in a weight ratio of 1:10 to 10: 1.
  • the active ingredients were administered as a 20% emulsion in a mixture of 70% by weight cyclohexanone, 20% by weight Nekanil ® IN (Lutensol ® AP6, detergent with emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight.
  • % Emulphor ® EL Emulphor ® EL (Emulan ® EL, emulsifier based on ethoxylated fatty alcohols) prepared and diluted with water according to the desired concentration.
  • Leaves of wheat seedlings ("Chancellor" variety) were first treated with the aqueous preparation of the active ingredients (containing 63 ppm). After about 24 hours, the plants were dusted with spores of wheat powdery mildew (Erysiphe graminis var. Tritici). The plants treated in this way were then incubated for 7 days at 20-22 ° C. and a relative atmospheric humidity of 75-80%. The extent of the fungal development was then determined.
  • the active ingredients were:
  • Emulphor ® EL Emulphor ® EL, emulsifiers tor based on ethoxylated fatty alcohols

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Thiazole And Isothizaole Compounds (AREA)

Abstract

L'invention concerne des dérivés d'acide phénylacétique de la formule (I) dans laquelle les substituants et l'indice ont la notation suivante: R1 désigne hydrogène et alkyle; R2 désigne cyano, nitro, trifluorométhyle, halogène, alkyle et alcoxy; m vaut 0, 1 ou 2, les restes R2 pouvant être différents, si m vaut 2; R3 désigne hydrogène, cyano, nitro, hydroxy, amino, halogène, alkyle, halogénure d'alkyle, alcoxy, halogénure d'alcoxy, alkylthio, alkylamino ou dialkylamino; R4 désigne hydrogène, cyano, nitro, hydroxy, amino, halogène, alkyle éventuellement substitué, alcoxy, alkylthio, alkylamino, dialkylamino, alcényle, alcényloxy, alcénylthio, alcénylamino, N-alcényl-N-alkylamino, alkinyle, alkinyloxy, alkinylthio, alkinylamino, N-alkinyl-N-alylamino, cycloalkyle éventuellement substitué, cycloalkyloxy, cycloalkylthio, cycloalkylamino, N-cycloalkyl-N-alkylamino, cycloalcényle, cycloalcényloxy, cycloalcénylthio, cycloalcénylamino, N-cycloalcényl-N-alkylamino, hétérocyclyle, hétérocyclyloxy, hétérocyclylthio, hétérocyclylamino, N-hétérocyclyl-N-alkylamino, aryle, aryloxy, arylthio, arylamino, N-aryl-N-alkylamino, hétaryle, hétaryloxy, hétarylthio, hétarylamino, N-hétaryl-N-alkylamino; R5 désigne hydrogène, alkyle éventuellement substitué, cycloalkyle, alcényle, alkinyle, alkylcarbonyle, alcénylcarbonyle, alkinylcarbonyle ou alkylsulfonyle, aryle éventuellement substitué, arylcarbonyle, arylsulfonyle, hétaryle, hétarylcarbonyle ou hétarylsulfonyle. L'invention concerne par ailleurs leurs sels, leur procédé de préparation, les produits intermédiaires utilisés à cet effet, et leur utilisation.
EP95906289A 1994-02-04 1995-01-03 Derives d'acide phenylthio acetique, leur procede de preparation, produits intermediaires utilises a cet effet, et agents les contenant Withdrawn EP0741698A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE4403446 1994-02-04
DE4403446 1994-02-04
DE4421181 1994-06-17
DE4421181 1994-06-17
PCT/EP1995/000014 WO1995021156A1 (fr) 1994-02-04 1995-01-03 Derives d'acide phenylthio acetique, leur procede de preparation, produits intermediaires utilises a cet effet, et agents les contenant

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EP0741698A1 true EP0741698A1 (fr) 1996-11-13

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Country Status (13)

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EP (1) EP0741698A1 (fr)
JP (1) JPH09508396A (fr)
CN (1) CN1143361A (fr)
AU (1) AU686304B2 (fr)
BR (1) BR9506718A (fr)
CA (1) CA2182406A1 (fr)
CZ (1) CZ231796A3 (fr)
HU (1) HUT76523A (fr)
IL (1) IL112480A0 (fr)
MX (1) MX9603175A (fr)
NZ (1) NZ278588A (fr)
SK (1) SK102296A3 (fr)
WO (1) WO1995021156A1 (fr)

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ATE201196T1 (de) * 1995-04-08 2001-06-15 Basf Ag Verfahren zur herstellung von weitgehend isomerenreinen alpha-bisoximen
AU6742196A (en) * 1995-08-15 1997-03-12 Novartis Ag Pesticidal indazole derivatives
AR004012A1 (es) 1995-10-10 1998-09-30 Basf Ag Derivados de acido fenilacetico, procedimientos para su obtencion, su uso para preparar composiciones para combatir animales u hongos nocivos, lascomposiciones asi obtenidas y los procedimientos de aplicacion de dichas composiciones.
JPH11514632A (ja) * 1995-11-02 1999-12-14 ビーエーエスエフ アクチェンゲゼルシャフト ピリジル酢酸誘導体、その製造方法ならびに製造用中間体、及びその用途
AU717468B2 (en) 1995-12-07 2000-03-30 Bayer Aktiengesellschaft Process for the preparation of pesticides
PL185913B1 (pl) 1995-12-07 2003-08-29 Bayer Ag Pochodne strobiluryny, sposób wytwarzania pochodnyPochodne strobiluryny, sposób wytwarzania pochodnych strobiluryny, związki pośrednie, sposób wytwarzch strobiluryny, związki pośrednie, sposób wytwarzania związków pośrednich, kompozycja pestycydowa oania związków pośrednich, kompozycja pestycydowa oraz zastosowanie pochodnych strobilurynyraz zastosowanie pochodnych strobiluryny
AU2178697A (en) * 1996-04-11 1997-10-29 Shionogi & Co., Ltd. Alpha-alkoxyiminobenzyl derivatives and agricultural chemicals containing them as active ingredients
CO5050364A1 (es) 1997-05-28 2001-06-27 Basf Ag Metodo para controlar hongos nocivos
US6313344B1 (en) 1998-05-27 2001-11-06 Bayer Aktiengesellschaft Organic compounds

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AU4639089A (en) * 1988-12-29 1990-08-01 Ciba-Geigy Ag Methyl esters of aldimino- or ketimino-oxy-ortho-tolylacrylic acid, manufacturing process and fungicides containing them
US5112860A (en) * 1989-11-16 1992-05-12 Basf Aktiengesellschaft Thiocarboxylic esters and fungicides containing them
US5187170A (en) * 1989-11-16 1993-02-16 Basf Aktiengesellschaft Thiocarboxylic esters and fungicides containing them
DE59108900D1 (de) * 1990-06-27 1998-01-22 Basf Ag O-Benzyl-Oximether und diese Verbindungen enthaltende Pflanzenschutzmittel

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Title
See references of WO9521156A1 *

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SK102296A3 (en) 1997-04-09
HUT76523A (en) 1997-09-29
WO1995021156A1 (fr) 1995-08-10
CN1143361A (zh) 1997-02-19
CA2182406A1 (fr) 1995-08-10
BR9506718A (pt) 1997-09-23
IL112480A0 (en) 1995-03-30
MX9603175A (es) 1997-04-30
CZ231796A3 (en) 1997-02-12
AU1454795A (en) 1995-08-21
JPH09508396A (ja) 1997-08-26
AU686304B2 (en) 1998-02-05
NZ278588A (en) 1997-04-24

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