EP1021399A2 - Fungizide mit hydroximsäuregruppen und hydrazongruppen - Google Patents

Fungizide mit hydroximsäuregruppen und hydrazongruppen

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Publication number
EP1021399A2
EP1021399A2 EP97943949A EP97943949A EP1021399A2 EP 1021399 A2 EP1021399 A2 EP 1021399A2 EP 97943949 A EP97943949 A EP 97943949A EP 97943949 A EP97943949 A EP 97943949A EP 1021399 A2 EP1021399 A2 EP 1021399A2
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EP
European Patent Office
Prior art keywords
group
formula
indicated
same definition
atom
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EP97943949A
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English (en)
French (fr)
Inventor
Philippe Desbordes
Christine Veyrat
Jean-Pierre Vors
Joseph Perez
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Bayer CropScience SA
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Aventis CropScience SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
    • C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
    • C07D249/12—Oxygen or sulfur atoms
    • 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
    • A01N37/36—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 singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • 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
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/04—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines without replacement of the other oxygen atom of the carboxyl group, e.g. imino-ethers
    • C07C257/06—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines without replacement of the other oxygen atom of the carboxyl group, e.g. imino-ethers having carbon atoms of imino-carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms, or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
    • C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
    • C07C259/06—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to hydrogen atoms or to acyclic carbon atoms

Definitions

  • the present invention relates to new compounds comprising a hydroximic or hydrazonic function, their use as fungicides, in particular in the form of a fungicidal composition, a process for controlling phytopathogenic fungi in crops using these compounds or compositions.
  • the derivatives comprising a hydroximic function used for the control of phytopathogenic fungi in cultures are known in particular from patents EP 463 488 and EP 370 629.
  • An object of the present invention is therefore to propose a new family of compounds comprising the hydroximic or hydrazonic function useful as fungicides.
  • Another object of the present invention is to provide a new family of compounds comprising the hydroximic or hydrazonic function having a broad spectrum of action improved on phytopathogenic fungi of cultures.
  • Another object of the present invention is to provide a new family of compounds comprising the hydroximic or hydrazonic function having a broad spectrum of action improved on phytopathogenic fungi of crops such as rice, cereals, fruit trees, vines and beet.
  • the invention relates to compounds comprising the hydroximic or hydrazonic function of general formula (I):
  • G is chosen from the groups Gl to G9
  • n 0 or 1
  • Ql is the nitrogen atom or the CH group
  • Q2 is the oxygen or sulfur atom
  • Q3 is the oxygen or sulfur atom
  • Q4 is the nitrogen atom or the group CR] ⁇
  • Q5 is the oxygen or sulfur atom or the group NR] 2
  • Y is the oxygen or sulfur atom or the amino (NH) or oxyamino (ONH) group
  • Wl is the oxygen or sulfur atom or the sulfinyl (SO) or sulfonyl (SO2) groups,
  • W2 is the oxygen atom or the NR13 group
  • X], X2, X3 are, independently of each other, a hydrogen atom, a halogen atom; or a hydroxy, mercapto, nitro, thiocyanato, azido, cyano or pentafluorosulfonyl group; a lower alkyl, lower haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyle, alkylthioalkyle, haloalkylthioalkyle, cyanoalkyle, cyanoalkoxy, cyanoalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl; or a lower cycloalkyl, lower halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alken
  • X4 is a hydrogen atom, a halogen atom; or a lower alkyl, lower haloalkyl, alkoxy, haloalkoxy group; or the cyano, nitro, R-, R2 are, independently of each other, a hydrogen atom, a lower alkyl group, lower haloalkyl, a lower cycloalkyl group, lower halocycloalkyl, an alkoxyalkyl group, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl; or a cyano, acyl, carboxy, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl group, a lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl,
  • R] and R2 may together form a radical which is equal to an alkylene group, optionally substituted by one or more halogen atoms, optionally substituted by one or more lower alkyl groups,
  • R3 is hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkvle, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl; or a nitro, cyano, acyl, carboxy, carbamoyl, N-alkylcarbamoyl, N.N-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxy-carbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl group; or an alkenyl, alkynyl, N, N-dialkylamino, N, N-dialkylaminoalkyl group
  • R4 is lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl; or an alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino group,
  • R5 is independently of each other a lower alkyl, lower haloalkyl group
  • R7 is a lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxvalkyle, alkenyl, alkynyl group
  • Rg is a lower alkyl, lower haloalkyl, alkoxyalkyl group. haloalkoxyalkyle, alkenyl, alkynyle, formyle, acyle,
  • R9 is hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl,
  • RjO is a halogen atom, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfmyl, haloalkylsulfinyl, alkylsulfonyl. haloalkylsulfonyl,
  • R-, R] _2 are independently of each other hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl,
  • R] _3 is hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, optionally substituted allyl group, optionally substituted propargyl group, benzyl group optionally substituted; or an acyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl group; or an optionally substituted alkylsulfonyl, haloalkylsulfonyl, arylsulfonyl group,
  • R5 is other than an alkyl group
  • R4 is other than an alkoxy group
  • alkylamino dialkylamino
  • R3 is other than hydrogen, alkyl, haloalkyl, cycloalkyl, halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, cyanoalkyl, alkenyl, alkynyl, dialkylaminoalkyl, or phenyl or benzyl possibly substituted.
  • the halogen atom means the fluorine, chlorine, bromine or iodine atom
  • the adjective "lower” qualifying an organic radical means that this radical has from 1 to 6 carbon atoms, with the exception of the cycloalkyl radical where the adjective “lower” means from 3 to 6 carbon atoms,
  • the alkyl radicals may be linear or branched, - the halogenated alkyl radicals may contain one or more identical or different halogen atoms,
  • acyl radical signifies alkylcarbonyl, or cycloalkylcarbonyl
  • acyl applies to the alkyl or cycloalkyl part of this radical
  • the two substituents can constitute a saturated or unsaturated nitrogen heterocycle, of 5 or 6 atoms,
  • the two substituents can constitute a saturated or unsaturated nitrogen heterocycle, of 5 or 6 atoms.
  • Preferred embodiments of the invention are those in which the products of formula (I) also have one and / or the other of the following characteristics, taken individually or in combination:
  • n 0 or 1 p ⁇ l
  • Q2 is the oxygen atom
  • / or Q3 is the oxygen atom
  • / or Q4 is the nitrogen atom
  • / or Q5 is the oxygen atom
  • Wl is the oxygen or sulfur atom
  • W2 is the oxygen atom or an alkylamino, haloalkylamino, alkoxyalkylamino, allylamino group
  • Y is the oxygen atom
  • X3 and X4 are independently of each other a hydrogen atom, a lower alkyl group, a halogen atom, or the cyano, trifluoromethyl, methoxy,
  • R ⁇ and R2 are, independently of each other, a hydrogen atom, a lower alkyl, lower cycloalkyl, lower haloalkyl, alkoxyalkyl, cyano, cyanoalkyl, N-alkylaminoalkyl, N, N-dialkylaminoalkyl, acylaminoalkyl, lower alkoxycarbonyl , N-alkylcarbamoyl, N, N- dialkylcarbamoyle,
  • R3 is a hydrogen atom, a lower alkyl, lower cycloalkyl, lower haloalkyl, alkoxyalkyl group, preferably a methyl, ethyl, propyl, isopropyl, cyclopropyl, methoxymethyl radical
  • R4 is a lower alkyl, alkoxy, alkylamino, dialkylamino group, preferably a methyl, ethyl, propyl, methoxy, ethoxy, methylamino radical.
  • R5, Rg, Rg and R9 are, independently of each other, a lower alkyl, lower haloalkyl group, preferably a methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl, propyl, radical.
  • R7 is a lower alkyl, lower haloalkyl group, preferably a methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl, propyl, an allyl, propargyl group
  • Rj O is a chlorine atom, a lower alkyl group, lower haloalkyl, preferably methyl, an alkoxy, alkylthio group, preferably methoxy, methylthio,
  • R] i and R] 2 are, independently of one another, a lower alkyl, lower haloalkyl, alkoxyalkyl, allyl, propargyl,
  • R 3 is hydrogen, lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, allyl, propargyl, benzyl.
  • Wl is the oxygen atom
  • R is the hydrogen atom or the methyl radical
  • R2 is a hydrogen atom or a lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N, N-dialkylaminoalkyl, lower alkoxycarbonyl, N.N-dialkyl-carbamoyl group,
  • the compounds of general formula (I) and the compounds which may be used as intermediates in the preparation processes, and which will be defined when describing these processes, may exist in one or more forms of geometric isomers depending on the number of double bonds of the compound.
  • the compounds of general formula (I) where G is the group G1, G2 or G3 may contain four different stereoisomers denoted (E, E), (E, Z), (Z, E), (Z, Z) depending on the configuration of the two double bonds.
  • the notation E and Z can be replaced respectively by the terms syn and anti, or cis and trans. We will refer in particular to the work of E.Eliel and S. Wilen “Stereochemistry of Organic Compounds” Ed. Wiley (1994) for the description and the use of these notations.
  • the compounds of general formula (I) where G is the group G4 to G9 can comprise two different stereoisomers denoted (E) or (Z) depending on the configuration of the hydroximic or hydrazonic group.
  • the compounds of general formula (I) and the compounds which may be used as intermediates in the preparation processes, and which will be defined when describing these processes, may exist in one or more forms of optical isomers or chiral depending on the number of asymmetric centers of the compound.
  • the invention therefore relates to all the optical isomers as well as their racemic mixtures and the corresponding diastereoisomers as a mixture or as separate.
  • the separation of diastereoisomers and / or optical isomers can be carried out according to methods known per se (E.Eliel ibid.).
  • the compounds of the present invention of general formula (I) and the compounds which may be used as intermediates in the preparation processes can be prepared by at least one of the general preparation methods described below: method A to L.
  • G is one of the groups Gl to G9, the groups Gl to G9 having the same definition as those indicated for the formula (I), X4 having the same definition as that indicated for the formula (I),
  • Vi is a halogen atom (preferably chlorine or bromine), an alkylsulfonate or haloalkylsulfonate group (preferably methylsulfonate or trifluoromethylsulfonate), arylsulfonate (preferably 4-methylphenylsulfonate),
  • halogen atom preferably chlorine or bromine
  • an alkylsulfonate or haloalkylsulfonate group preferably methylsulfonate or trifluoromethylsulfonate
  • arylsulfonate preferably 4-methylphenylsulfonate
  • the suitable solvent for this reaction can be an aliphatic hydrocarbon such as pentane, hexane, heptane, octane; an aromatic hydrocarbon such as benzene, toluene, xylenes, halobenzenes; an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane; a halogenated hydrocarbon such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane; an ester such as methyl acetate, ethyl acetate, a nitrile such as acetonitrile, propionitrile, benzonitrile; a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylprolyleneurea, dimethylsulfoxide; or water.
  • the reaction time depends on the conditions used and is generally between 0.1 to 48 h.
  • alkali and alkaline earth metal hydroxides such as sodium, potassium, cesium or calcium hydroxide
  • alkali and alkaline earth alcoholates such as potassium ter-butoxide, alkali and alkaline earth hydrides, such as sodium, potassium or cesium hydride
  • alkali and alkaline earth metal carbonates and bicarbonates such as sodium, potassium, calcium carbonate or sodium, potassium or calcium bicarbonate
  • organic bases preferably nitrogen, such as pyridine, alkylpyridines, alkylamines such as trimethylamine, triethylamine or diisopropylethylamine, aza derivatives such as 1.5-diazabicyclo [4.3.0] non-5-ene or l, 8 -diazabicyclo [5.4.0] undec-7-ene.
  • the compounds of general formula (I) are obtained in the form of a variable mixture of isomers (E) and (Z) or of a single isomer (E) or of a single isomer (Z) depending on the configuration of the hydroximic or hydrazonic group. If necessary, the compounds of general formula (I) and of configuration (E) or (Z) depending on the configuration of the hydroximic or hydrazonic group, can be isolated and purified according to methods known per se such as for example extraction, crystallization or chromatography.
  • Condensation between the compound of formula (IV) and compound of formula (V) is carried out in the presence of an organic or inorganic base, or of a dehydration reagent such as anhydrides of carboxylic acids, preferably acetic anhydride or propionic anhydride, in the absence or in the presence of a solvent.
  • a dehydration reagent such as anhydrides of carboxylic acids, preferably acetic anhydride or propionic anhydride
  • R] R2, X], X2, X3 having the same definition as that indicated for formula (I), and U2 is a halogen atom (preferably chlorine or bromine), an alkylsulfonate group (preferably methylsulfonate or trifluoromethylsulfonate ), with a hydroxamic acid derivative where W2 is the oxygen atom or a hydrazonic acid derivative where W2 is the group NR13, R3 and R13 having the same definition as that indicated for formula (I), of formula (VII):
  • (VII) is carried out in the presence of an organic or inorganic base, in the absence or in the presence of a solvent.
  • G is one of the groups Gl to G9, the groups Gl to G9 having the same definition as that indicated for formula (I), X4 having the same definition as that indicated for the formula (I) and V] is a halogen atom (preferably chlorine or bromine), an alkylsulfonate group (preferably methylsulfonate or trifluoromethyl-sulfonate), arylsulfonate (preferably 4-methylphenylsulfonate), will be by convention, for the following of the description of the preparation methods, designated by the generic term "benzyles halide derivatives".
  • benzyl halide derivatives of formula (II) A where Vj is a halogen atom (preferably chlorine or bromine) can be obtained by halogenation of a compound of formula (VIII):
  • G is one of the groups G1 to G9, the groups G1 to G9 having the same definition as that indicated for the formula (I), X4 having the same definition as that indicated for the formula (I).
  • the halogenation of the compound of formula (VIII) can be carried out by radical, thermal or photochemical route, the various processes not being mutually exclusive, with an N-haloacetamide such as N-bromosuccinimide, N-chlorosuccinimide , N-bromoacetamide, in an inert solvent such as benzene or carbon tetrachloride or in the absence of a solvent with or without a free radical initiator at a temperature of 20 ° C to 170 ° C, preferably 80 ° C at 100 ° C according to J. March ibid. pages 689-697.
  • the benzyl halide derivatives of formula (II) A where V ⁇ is a halogen atom (preferably chlorine or bromine) can also be obtained by halogenation of a compound of formula (II) B:
  • G is one of the groups G1 to G9, the groups G1 to G7 having the same definition as that indicated for formula (I) and R4 is the group alkylamino, dialkylamino, the groups G8 and G9 having the same definition as that indicated for formula (I), X4 having the same definition as that indicated for formula (I), Wj is the oxygen atom, with a halogenating agent such as thionyl chloride, phosphorus oxytrichloride , phosphorus tribromide according to J. March ibid. pages 431-433 or with the lithium halide / mesyl halide / collidine reagent according to J. Org. Chem. (1971), 36.3044.
  • a halogenating agent such as thionyl chloride, phosphorus oxytrichloride , phosphorus tribromide according to J. March ibid. pages 431-433 or with the lithium halide / mesyl halide / collidine reagent
  • benzyl halide derivatives of formula (II) A where Vj is a halogen atom (preferably chlorine or bromine) can also be obtained by cleavage of a compound of formula (II) C:
  • G is one of the groups G1 to G9, the groups G1 to G7 having the same definition as that indicated for formula (I) and R4 is the group alkylamino, dialkylamino, the groups G8 and G9 having the same definition as that indicated for formula (I), X4 having the same definition as that indicated for formula (I), W] is the oxygen atom, and P is a protecting group for the alcohol function as an ester preferably acetic or benzoic, or an ether preferably methyl, methoxymethyl, phenyl, benzyl, (we will refer advantageously to the work "Protective Groups in Organic Synthesis" by W. Greene and P.Wuts, Ed. Wiley (1991) for the choice and preparation of said protective groups), with a Lewis acid such as boron tribromide, or anhydrous hydracids such as hydrogen chloride.
  • This cleavage reaction is known in particular according to patent EP 525516
  • benzyl halide derivatives of formula (II) A and the compounds of formula (VIII), (II) B and (II) C can be prepared according to methods known per se. These different methods or the related prior art will be explained in methods J, K and L.
  • the groups Gl to G7 having the same definition as that indicated for formula (I) and R4 is the group or radical amino, alkylamino, dialkylamino.
  • the groups G8 and G9 having the same definition as that indicated for the formula (I), X4 having the same definition as that indicated for the formula (I) can be obtained by a process consisting in bringing a compound of formula ( II) B in which G is one of the groups G1 to G9, the groups G1 to G7 having the same definition as that indicated for formula (I) and R4 is the group or radical amino, alkylamino, dialkylamino, the groups G8 and G9 having the same definition as that indicated for formula (I), X4 having the same definition as that indicated for formula (I), and Wi is the oxygen or sulfur atom,
  • This reaction is carried out in the presence of an organic or inorganic base, in the absence or in the presence of a solvent.
  • the reaction is generally carried out at a temperature between - 80 ° C and 180 ° C (preferably between 0 ° C and 150 ° C) or at the boiling point of the solvent used.
  • the solvent suitable for this reaction can be an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, a nitrile such as acetonitrile, propionitrile, benzonitrile, a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimé hylprolylène urea, or dimethylsulfoxide. Mixtures of these different solvents can also be used.
  • an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane
  • a nitrile such as acetonitrile, propionitrile, benzonitrile
  • a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimé hyl
  • the reaction time depends on the conditions used and is generally between 0.1 to 48 h.
  • organic or inorganic base suitable for this reaction mention may be made of hydrides of alkali and alkaline earth metals, such as sodium, potassium or cesium hydride, alcoholates of alkali and alkaline earth metals, such as tert-butoxide of potassium.
  • the compounds of general formula (I) are obtained in the form of a variable mixture of isomers (E) and (Z) or of a single isomer (E) or of a single isomer (Z) depending on the configuration of the hydroximic or hydrazonic group. If necessary, the compounds of general formula (I) and of configuration (E) or (Z) depending on the configuration of the hydroximic or hydrazonic group, can be isolated and purified according to methods known per se such as for example extraction, crystallization or chromatography.
  • the thiohydroxamic acids of formula (III) A where Wl is the sulfur atom and W2 is the oxygen atom or the thiohydrazonic acids of formula (III) A where Wl is the sulfur atom and W2 is the group NR13 , Ri, R2, R3, R13, X ⁇ , X2, X3 and p having the same definition as that indicated for formula (I), are also the object of the present invention.
  • R4 is the alkoxy, alkylamino, dialkylamino group, the other substituents having the same definition as that indicated for formula (I), with a Wittig-Horner reagent of formula (X) A:
  • R ⁇ being a lower alkyl or lower haloalkyl group
  • R ⁇ being a lower alkyl, phenyl or benzyl group
  • R ⁇ being a lower alkyl or lower haloalkyl group
  • R ⁇ being an optionally substituted phenyl group.
  • Hal " being a halide ion, by the action of one or more equivalents of a base such as alkali or alkaline earth alcoholates, preferably sodium ethylate, sodium methylate or potassium tert-butoxide, hydrides of alkali and alkaline earth metals, preferably sodium or potassium hydride, of an organometallic derivative such as alkyllithians, preferably butyllithium, alkylmagnesium halides or lithium diisopropylamide in an aprotic solvent such as ethers, preferably diethyl ether or tetrahydrofuran at a temperature of - 78 ° C to 50 ° C preferably - 70 ° C to 20 ° C according to J.March ibid, pages 956-963 or patent WO 9529896.
  • the Wittig-Horner reagents of formula (X) A and the Wittig reagents of formula (X) B can be obtained according to methods known per se.
  • T is the oxygen atom and M is an alkaline or alkaline earth ion
  • Ql being the nitrogen atom or the CH group
  • R4 is the alkoxy group. alkylamino, dialkylamino, the other substituents having the same definition as that indicated for formula (I), with a reagent of formula (XIII):
  • W ⁇ is a halogen atom (preferably chlorine or bromine), R5 having the same definition as that indicated for formula (I), by the action of one or more base equivalents such as the hydroxides of alkali metals or alkaline earth, alkali or alkaline earth alcoholates, alkali and alkaline earth hydrides, carbonates and bicarbonates of alkali or alkaline earth metals, optionally in the presence of a phase transfer catalyst such as quaternary ammonium, in a solvent aprotic such as ethers preferably diethyl ether or tetrahydrofuran at a temperature of -78 ° C to 40 ° C preferably between -20 and 25 ° C.
  • a phase transfer catalyst such as quaternary ammonium
  • R4 is the alkoxy, alkylamino, dialkylamino, X4 group having the same definition as that indicated for formula (I),
  • V1 is a halogen atom (preferably chlorine or bromine), an alkylsulfonate group (preferably methylsulfonate or trifluoromethylsulfonate), arylsulfonate (preferably 4-methylphenylsulfonate),
  • the compounds of general formula (I) for which G is the group G 1 to G7 and R4 is the alkylamino or dialkylamino group, the other substituents having the same definition as that indicated for formula (I), can be obtained by a process consisting in bringing into contact a compound of general formula (I) for which G is the group G1 to G7 and R4 is the alkoxy or alkylthio group, the other substituents having the same definition as that indicated for formula (I), with an alkylamine or dialkylamine, preferably methylamine, in an alcoholic solvent such as methanol, ethanol, propanol or isopropanol, at a temperature of - 50 ° C to 100 ° C or at the boiling point of the chosen solvent .
  • an alkylamine or dialkylamine preferably methylamine
  • an alcoholic solvent such as methanol, ethanol, propanol or isopropanol
  • the compounds of general formula (I) for which W1 is the sulfoxide (SO) or sulfone (SO2) group and G being one of the groups Gl, G3. G4, G6 to G9, Q2 and Q3 being the oxygen atom, the other substituents having the same definition as that indicated for formula (I), can be obtained by oxidation of the compounds of general formula (I) for which Wl is the sulfur atom, G being one of the groups Gl, G3, G4, G6 to G9, Q2 and Q3 being the oxygen atom, the other substituents having the same definition as that indicated for the formula (I ), using one or more equivalent of an oxidizing agent such as organic peroxides, preferably peracetic acid, 3-chloroperbenzoic acid, mineral peroxides, hydroperoxides such as hydrogen peroxide, oxychlorides minerals or oxygen, in the presence or absence of a catalyst in an inert solvent according to J. Mardi ibid. pages 1201-1203.
  • Method I
  • the reaction time is chosen so as to obtain a total conversion of the cis isomer into the trans isomer.
  • the reaction is generally carried out at a temperature between 0 ° C and the boiling point of the solvent.
  • the suitable solvent for this reaction can be an aliphatic hydrocarbon such as pentane, hexane, heptane, octane; an aromatic hydrocarbon such as benzene, toluene, xylenes, an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane; a halogenated hydrocarbon such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane; an ester such as methyl acetate, ethyl acetate; a nitrile such as acetonitrile, propionitrile, benzonitrile; an alcohol such as methanol, ethanol, propanol, isopropanol; a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylproly
  • the solvent will preferably be an aromatic solvent such as toluene or xylenes or an ether such as diisopropyl ether.
  • the catalyst preferably an acid catalyst, will be chosen from anhydrous hydracids such as hydrogen chloride, carboxylic acids such as acetic acid, propionic acid, trifluoroacetic acid, sulfonic acids such as methanesulfonic acid, trifiuorométhanesulfonique, 4-methylphenylsulphonique or sulfuric acid.
  • benzyl halide derivatives of formula (II) A and the compounds of formula (VIII), (II) B and (II) C can be prepared according to very numerous methods known per se.
  • benzyl halide derivatives of formula (II) A and the like where G is the group G1 or G2 of stereochemistry (E) or (Z), can be prepared according to this which is described in patents EP 426460, EP 398692, EP 617014, EP 585751, EP 487409, EP 535928, DE 4305502,
  • X4 having the same definition as that indicated for formula (I) and V 1 is a halogen atom preferably chlorine or bromine according to the process described in method A.
  • Y, X4, Q2, R4 and Rg have the same meaning as for formula (I) and Rc is a hydrogen atom or a lower alkyl group optionally substituted by one or more halogens or an alkoxy group, a benzyl optionally substituted, optionally substituted aryl, by reaction with a halogenating agent.
  • This reaction can be carried out at a temperature between -30 ° C and 50 ° C in an inert solvent.
  • inert solvent is meant an aliphatic hydrocarbon such as pentane, hexane, cyclohexane and petroleum ether; or an aromatic compound such as toluene, xylenes; or alternatively chlorinated compounds such as methylene chloride, chloroform, 1,1,1-trichloroethane and chlorobenzene; or alternatively ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran; or a nitrile such as acetonitrile or propionitrile.
  • halogenating agent it is possible to use, for example, a Lewis acid such as Aluminum chloride, Boron trichloride, or a halogenated hydracid such as hydrogen chloride or hydrogen bromide.
  • a Lewis acid such as Aluminum chloride, Boron trichloride
  • a halogenated hydracid such as hydrogen chloride or hydrogen bromide.
  • the halogenating agent will be in equimolar amount or in excess.
  • Y, X4, Q2 and R4 have the same meaning as for formula (I) and Rc is a hydrogen atom or a lower alkyl group optionally substituted by one or more halogens or an alkoxy group, an optionally substituted benzyl, an optionally substituted aryl.
  • alkylating agent an alkyl or acyl halide or sulfonate of formula (XV) will be used:
  • Rg is a lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, formyl or acyl group
  • Vj is a halogen atom (preferably bromine or iodine), an alkylsulfonate group (preferably trifluoromethylsulfonate), arylsulfonate,
  • reaction is carried out in a dipolar aprotic solvent such as amides such as dimethylformamide, dimethylacetamide, N-methylpyrolidone at a temperature between - 70 ° C and 180 ° C, preferably between - 30 ° C and 80 ° C.
  • a dipolar aprotic solvent such as amides such as dimethylformamide, dimethylacetamide, N-methylpyrolidone
  • a reducing agent such as an alkali or alkaline hydride preferably earth sodium borohydride in an alcohol such as methanol, ethanol, propanol, isopropanol. butanol, tertiobutanol according to J. March ibid. page 910.
  • V is a halogen atom preferably chlorine or bromine, with a mineral carboxylate such as a formate, an acetate, a propionate or other salt mineral of lower alkylcarboxylic acid, the alkyl group of which may be optionally substituted by one or more halogens or an alkoxy group or an optionally substituted phenyl, or else a benzoic acid salt optionally substituted according to J.March ibid.p398.
  • a mineral carboxylate such as a formate, an acetate, a propionate or other salt mineral of lower alkylcarboxylic acid, the alkyl group of which may be optionally substituted by one or more halogens or an alkoxy group or an optionally substituted phenyl, or else a benzoic acid salt optionally substituted according to J.March ibid.p398.
  • the reaction is preferably carried out in a dipolar aprotic solvent such as the amides, preferably formamide, acetamide, dimethylacetamide, N-methylpyrrolidine, at a temperature ranging from 0 ° to reflux of the solvent.
  • a dipolar aprotic solvent such as the amides, preferably formamide, acetamide, dimethylacetamide, N-methylpyrrolidine, at a temperature ranging from 0 ° to reflux of the solvent.
  • This process consists in bringing into contact the intermediaries of general formula (III) A in which the groups W1, W2, R ⁇ , R2, R3, R13, X ⁇ , Xi, X3, and p have the same meaning as for the formula (I), with a compound of general formula (II) A for which G is the group G3, Rg is the trifluoromethyl radical, X4, R4 and Q2 having the same definition as that indicated for formula (I) and Vi is a halogen atom, preferably chlorine or bromine according to the process described in method A.
  • the compounds of general formula (II) A for which G is the group G3, Rg is the trifluoromethyl radical, X4, R4 and Q2 having the same definition as that indicated for formula (I) and V] is a halogen atom preferably chlorine or bromine can be obtained by halogenation of the compounds of general formula (VIII) for which G is the group G3, Rg is the trifluoromethyl radical, X4, R4 and Q2 having the same definition as that indicated for formula (I) , according to the method described in method A.
  • Rg is the trifluoromethyl radical, X4, R4 and Q2 having the same definition as that indicated for formula (I), can be obtained by dehydration of the compounds of formula (XVI):
  • a dehydrating agent such as anhydrous hydracids (preferably sulfuric acid), their alkali or alkaline earth salts (preferably potassium hydrogen sulfate) or anhydrides such as phosphoric anhydride according to J.March ibid. pages 101 1 et seq. or Chem.Ber. (1986) ,!
  • alkylsulfonate chlorides preferably methylsulfonate or trifluoromethylsulfonate
  • arylsulfonate chlorides preferably 4-methylphenylsulfonate
  • a nitrogenous base such as pyridine, alkylpyridines, alkylamines such as trimethylamine, triethylamine or diisoprylethylamine TetrahedromAsymmetry (1990),!, 521
  • dialkyldiazodicarboxylates preferably diethyldiazodicarboxylate
  • a triarylphosphine such as diphenylphophine according to J. Org. Chem. (1984), 49, 1430.
  • This reaction is carried out in the absence or in the presence of a solvent.
  • the reaction is generally carried out at a temperature between - 80 ° C and 180 ° C (preferably between 0 ° C and 150 ° C) or at the boiling point of the solvent used.
  • the solvent suitable for this reaction can be a halogenated hydrocarbon such as dichloromethane, chloroform, 1, 2-dichloroethane, 1,1,1, -trichloroethane, an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, a nitrile such as acetonitrile, propionitrile, benzonitrile, a nitrogenous base such as pyridine, alkylpyridines, a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylprolylene urea, or dimethylsulfoxide
  • the reaction time depends on the conditions used and is generally between 0.1 to 48 h.
  • the compounds of general formula (XVI) in which X4, R4 and Q2 have the same meaning as that indicated for formula (I), can be obtained by aldolic condensation reaction of the compounds of formula (XVII):
  • a base such as alkali and alkaline earth hydrides, preferably sodium or potassium hydride, alkali and alkaline earth alcoholates, of an organometallic derivative such as the alkylllithians, preferably the butyllithium, alkyl magnesium halides or amides of alkali and alkaline earth metals such as lithium diisopropylamide or lithium amide of hexamethyldisilazane, in an aprotic solvent such as ethers preferably diethyl ether or tetrahydrofuran at a temperature from - 78 ° C to 50 ° C preferably - 70 ° C to 20 ° C
  • a base such as alkali and alkaline earth hydrides, preferably sodium or potassium hydride, alkali and alkaline earth alcoholates, of an organometallic derivative such as the alkylllithians, preferably the butyllithium, alkyl magnesium halides or amides of alkali and alkaline earth
  • the invention also relates to fungicidal compositions comprising an effective amount of at least one active material of formula (I).
  • the fungicidal compositions according to the invention comprise, in addition to the active material of formula (I), solid or liquid carriers, acceptable in agriculture and / or surfactants also acceptable in agriculture.
  • the supports can be used inert and usual and the usual surfactants.
  • fungicidal compositions according to the invention can also contain all kinds of other ingredients such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, stabilizers, sequestrants, etc. More generally, the active ingredients can be combined with any solid or liquid additive corresponding to the usual techniques of formulation.
  • compositions according to the invention usually contain from 0.05 to 95% (by weight) of active material, one or more solid or liquid supports and, optionally, one or more surfactants.
  • support in the present description, is meant an organic or mineral, natural or synthetic material, with which the active material is combined to facilitate its application on the parts of the plant. This support is therefore generally inert and it must be acceptable in agriculture.
  • the support can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, in particular butanol etc.).
  • the surfactant can be an emulsifying, dispersing or wetting agent of ionic or nonionic type or a mixture of such surfactants.
  • the presence of at least one surfactant is generally essential when the active material and / or the inert support are not soluble in water and the vector agent for the application is water.
  • compositions for agricultural use according to the invention can contain the active material within very wide limits, ranging from 0.05% to 95% (by weight).
  • Their surfactant content is advantageously between 5% and 40% by weight. Unless otherwise indicated, the percentages given in this description are percentages by weight.
  • compositions according to the invention are themselves in fairly diverse forms, solid or liquid.
  • powders for dusting with an active material content of up to 100%
  • granules in particular those obtained by extrusion, by compacting, by impregnation of a granulated support, by granulation. from a powder (the active material content in these granules being between 0.5 and 80% for the latter cases).
  • the fungicidal compositions according to the invention can also be used in the form of powders for dusting; one can also use compositions comprising 50 g of active material and 950 g of talc; one can also use compositions comprising 20 g of active material, 10 g of finely divided silica and 970 g of talc; these constituents are mixed and ground and the mixture is applied by dusting.
  • liquid compositions or intended to constitute liquid compositions during application, mention may be made of solutions, in particular water-soluble concentrates, emulsions, concentrated suspensions, wettable powders (or spray powder) .
  • the concentrated suspensions are prepared so as to obtain a stable fluid product which does not deposit and they usually contain from 10 to 75% of active material, from 0.5 to 15% of surfactants, from 0.1 to 10% of thixotropic agents. from 0 to 10% of suitable additives, such as defoamers, corrosion inhibitors, stabilizers, penetrating agents and adhesives and, as support, water or an organic liquid in which the active ingredient is poorly or not soluble: some organic solids or mineral salts may be dissolved in the carrier to help prevent sedimentation or as antifreeze for water.
  • organopolysiloxane oil (antifoam) 1 g
  • polysaccharide 1.5 g
  • Wettable powders are usually prepared so that they contain 20 to 95% of active ingredient, and they usually contain, in addition to the solid support, 0 to 30% of a wetting agent, 3 20% of a dispersing agent, and, when necessary, 0.1 to 10% of one or more stabilizers and / or other additives, such as penetrating agents, adhesives, or anti-caking agents, dyes, etc.
  • the active materials are intimately mixed in the appropriate mixers with the additional substances and ground with mills or other suitable grinders.
  • Example PM 2 - active ingredient 10%
  • This wettable powder contains the same ingredients as in the previous example, in the following proportions: - active material 75%
  • aqueous dispersions and emulsions for example the compositions obtained by diluting a wettable powder according to the invention with water, are included in the general scope of the present invention.
  • the emulsions can be of the water-in-oil or oil-in-water type and they can have a thick consistency like that of a "mayonnaise".
  • the fungicidal compositions according to the invention can be formulated in the form of water-dispersible granules also included within the scope of the invention.
  • the active material content of these granules is generally between approximately 1% and 95%, and preferably between 25% and 90%.
  • the rest of the granule is essentially composed of a solid filler and optionally surfactant additives giving the granule properties of dispersibility in water.
  • These granules can be essentially of two distinct types depending on whether the selected filler is soluble or not in water.
  • the filler When the filler is water-soluble, it can be mineral or, preferably, organic. Excellent results have been obtained with urea.
  • an insoluble filler it is preferably mineral, such as for example kaolin or bentonite.
  • surfactants at a rate of 2 to 20% by weight of the granule of which more than half is, by example, consisting of at least one dispersing agent, essentially anionic, such as an alkaline or alkaline earth polynaphthalene sulfonate or an alkaline or alkaline earth lignosulfonate, the remainder consisting of nonionic or anionic wetting agents such as an alkyl naphthalene sulfonate alkaline or alkaline earth.
  • dispersing agent essentially anionic, such as an alkaline or alkaline earth polynaphthalene sulfonate or an alkaline or alkaline earth lignosulfonate
  • nonionic or anionic wetting agents such as an alkyl naphthalene sulfonate alkaline or alkaline earth.
  • the granule according to the invention can be prepared by mixing the necessary ingredients and then granulation according to several techniques known per se (bezel, fluid bed, atomizer, extrusion, etc.). It generally ends with a crushing followed by sieving to the particle size chosen within the limits mentioned above. It is also possible to use granules obtained as above and then impregnated with a composition containing the active material. Preferably, it is obtained by extrusion, operating as indicated in the examples below.
  • Example GDI Dispersible granules
  • a mixer 90% by weight of active material and 10% urea pearls are mixed. The mixture is then ground in a pin mill. A powder is obtained which is moistened with approximately 8% by weight of water. The wet powder is extruded in a perforated roller extruder. A granule is obtained which is dried, then crushed and sieved, so as to keep respectively only the granules of a size between 150 and 2000 microns.
  • Example GD2 Dispersible granules
  • These granules can be used alone, in solution or dispersion in water so as to obtain the desired dose. They can also be used to prepare combinations with other active materials, in particular fungicides, the latter being in the form of wettable powders, or aqueous granules or suspensions.
  • the compounds of the invention can also be mixed with one or more insecticides, fungicides, bactericides, attractant acaricides or pheromones or other compounds with biological activity.
  • the mixtures thus obtained have a broad spectrum activity.
  • Mixtures with other fungicides are particularly advantageous, in particular mixtures with carbendazim, thiuram, dodine, maneb, mancozeb, benomyl, cymoxanil, fenpropidine, fenpropimorph, triadimefon, captan, captafol .
  • compositions according to the invention are useful for treating cereal seeds (wheat, rye, triticale and barley in particular), potato, cotton, peas, rapeseed, corn, flax or even seeds of forest trees (especially conifers).
  • seed treatment actually refers to the treatment of seeds.
  • the application techniques are well known to those skilled in the art and they can be used without disadvantage in the context of the present invention. Mention may be made, for example, of film-coating or coating.
  • Another subject of the invention is a method for combating, for curative or preventive purposes, phytopathogenic fungi in crops, characterized in that one applies to the seeds of plants or to the leaves of plants or to soils where 'We make or where we want to grow plants, an effective (agronomically effective) and non-phytotoxic amount of an active material of formula (I), preferably in the form of a fungicidal composition according to the invention.
  • effective and non-phytotoxic amount means an amount of composition according to the invention sufficient to allow the control or destruction of the fungi present or likely to appear on the cultures, and not causing for said cultures any significant symptom of phytotoxicity. Such an amount is likely to vary within wide limits depending on the fungus to be combated, the type of crop, the climatic conditions, and the compounds included in the fungicidal composition according to the invention. This quantity can be determined by systematic field tests, within the reach of those skilled in the art.
  • the invention relates to a method of protection, for preventive or curative purposes, of plant multiplication products, as well as of the plants resulting therefrom, against fungal diseases, characterized in that said products are covered with an effective dose and not phytotoxic of a composition according to the invention.
  • compositions according to the invention can also be applied as a foliar application on plant crops.
  • - wheat with regard to the control of the following seed diseases: Fusarium wilt (Microdochium nivale and Fusarium roseum), caries (Tilletia caries. Tilletia controversa or Tilletia indica). septoria (Septoria nodorum); - wheat, with regard to the fight against the following diseases of the aerial parts of the plant: the foot rot (Pseudocercosporella herpotricho ⁇ des), the foot scald (Gaeumannomyces graminis), fusariosis of the foot ⁇ F. culmorum, F.
  • the foot rot Pseudocercosporella herpotricho ⁇ des
  • helminthosporioses Pyrenophora teres and Cochliobolus sativus
  • powdery mildew Erysiphe graminis forma specie horde ⁇
  • dwarf rust Puccinia hordei
  • rhynchosporiosis Rhynchosporium secalis
  • Rhizoctonia solani Fusarium solani
  • certain viral infections virus Y
  • - pea as regards the fight against the following seed diseases: anthracnose (Ascochyta pisi, Mycosphaerella pinodes), fusarium wilt (Fusarium oxysporum), gray rot (Botrytis cinerea); - rapeseed, as regards the fight against the following seed diseases: Phoma lingam and Alternaria bra sicae;
  • the dose of composition applied is. in general, advantageously such that the dose of active material is between 2 and 200 g of active material per 100 kg of seed, preferably between 3 and 150 g per 100 kg in the case of seed treatments.
  • doses of 10 to 800 g / ha, preferably 50 to 300 g / ha are generally applied as a foliar treatment.
  • n D 1.5270 (23 ° C) (these expressions denote the refractive index at 23 ° C using the D line of sodium as light).
  • reaction mixture After heating at 40 ° C for 2 days, the reaction mixture is filtered, diluted with water and re-extracted with ether. After purification by chromatography on silica, 2.5 g of the expected compound are obtained in the form of a yellow oil.
  • Step 1
  • Step 3 Preparation of (E, Z) -2-methoxyimino-2- [2- [l- (l- (methoxycarbonyl) -l-
  • Step 5 Preparation of (E, E) -2-methoxyimino-N-methyl-2- [2- [1- (1- (methoxycarbonyl) -1- (phenyl) ethyloxyimino) ethyloxymethyl] phenyl] acetamide
  • Step 1
  • the reaction medium is heated at 55 ° C for 3 hours and then poured into 100 ml of water.
  • the pH is brought to 7 by adding IN hydrochloric acid and the aqueous phase reextracted with ethyl acetate, washed with water and dried over magnesium sulfate. Evaporation of the solvents leaves 0.6 g of a yellow oil. Trituration with a minimum of diisopropyl ether gives 0.31 g of the expected compound in the form of a white solid. Mp 144 ° C.
  • Step 1
  • Step 2 Preparation of (E, E) -2- [2- [1- (1- (phenyl) ethyloxyimino) ethyloxymethyl] - phenyl] -but-2-enoate
  • Example B1 In vivo test on Plasmopara viticola (downy mildew):
  • aqueous suspension of the active ingredient to be tested having the following composition is prepared by fine grinding: - active ingredient: 60 mg
  • Vine cuttings (Vitis vinifera), Chardonnay variety, are grown in pots. When these plants are 2 months old (8 to 10 leaf stage, 10 to 15 cm high), they are treated by spraying with the above aqueous suspension.
  • Plants, used as controls are treated with an aqueous solution not containing the active ingredient.
  • each plant After drying for 24 hours, each plant is contaminated by spraying with an aqueous suspension of Plasmopara viticola spores obtained from a culture of 4-5 days, then suspended at the rate of 100,000 units per cm.
  • the contaminated plants are then incubated for two days at around 18 ° C, in an atmosphere saturated with humidity and then for five days at around 20-22 ° C under 90-100% relative humidity. The reading is done seven days after contamination, in comparison with the control plants.
  • Example B2 In vivo test on Puccinia recondita (wheat rust):
  • aqueous suspension of the active ingredient to be tested having the following composition is prepared by fine grinding: - active ingredient: 60 mg
  • each plant is contaminated by spraying with an aqueous suspension of spores (150,000 spores per cm- 3 ) of Puccinia recondita.
  • This suspension is obtained from contaminated plants. Contaminated wheat plants are then incubated for 24 hours at approximately 20 ° C, in an atmosphere saturated with humidity and then for seven to fourteen days at 60%> relative humidity.
  • the reading is between the 8 th and 15 th day after the contamination, in comparison with the control plants. Under these conditions, a good protection is observed at a dose of 40 ppm.
  • Example B3 In vivo test on Septoria tritici (wheat septoria):
  • aqueous suspension of the active ingredient to be tested having the following composition is prepared by fine grinding: - active ingredient: 60 mg - Tween 80 surfactant (oleate of polyoxyethylene derivative of sorbitan) diluted to 10% in water: 0.3 ml
  • Wheat (Scipion variety) in pots, sown on a 50/50 peat soil pozzolan peat substrate and maintained at 12 ° C, is treated at the 1 leaf stage (10 cm in height) by spraying the above aqueous suspension. Plants, used as controls are treated with an aqueous solution not containing the active ingredient.
  • each plant is contaminated by spraying with an aqueous suspension of spores (500,000 spores per cm 3) of Septoria tritici.
  • the spores are harvested from a seven-day-old culture. Contaminated wheat plants are incubated for 72 hours at
  • the reading is done twenty-one days after the contamination, in comparison with the control plants. Under these conditions, a good protection is observed at a dose of 40 ppm.
  • Example B4 In vivo test on Septoria nodorum (wheat septoria):
  • An aqueous suspension of the active material to be tested having the following composition is prepared by fine grinding:
  • aqueous suspension is then diluted with water so as to obtain the desired concentration in ppm (parts per million).
  • Wheat (Scipion variety) in pots, sown on a 50/50 peat soil pozzolan peat substrate and maintained at 12 ° C, is treated at the 1 leaf stage (10 cm in height) by spraying the above aqueous suspension.
  • Plants, used as controls are treated with an aqueous solution not containing the active ingredient.
  • each plant is contaminated by spraying with an aqueous suspension of spores (500,000 spores per cm J ) of Septoria nodorum.
  • the spores are harvested from a seven-day-old culture.
  • Contaminated wheat plants are incubated for 72 hours at approximately 20 ° C, in a humid atmosphere and then for fourteen days at 90% relative humidity.
  • the reading is done fifteen days after contamination, in comparison with the control plants.
  • Example B5 In vivo test on Erisyphe graminis fsp tritici (wheat powdery mildew):
  • An aqueous suspension of the active material to be tested having the following composition is prepared by fine grinding:
  • This aqueous suspension is then diluted with water so as to obtain the desired concentration in ppm (parts per million).
  • Plants, used as controls are treated with an aqueous solution not containing the active ingredient.
  • the wheat plants are dusted with Erisyphe graminis spores, the dusting being carried out using diseased plants.
  • the reading is made seven to fourteen days after contamination, in comparison with the control plants.
  • Example B6 In vivo test on Erisyphe graminis fsp hordei (barley powdery mildew):
  • An aqueous suspension of the active material to be tested having the following composition is prepared by fine grinding:
  • This aqueous suspension is then diluted with water so as to obtain the desired concentration in ppm (parts per million).
  • Plants, used as controls are treated with an aqueous solution not containing the active ingredient.
  • the barley plants are dusted with Erisyphe graminis spores, the dusting being carried out using diseased plants.
  • the reading is made seven to fourteen days after contamination, in comparison with the control plants.
  • Example B7 In vivo test on Pyrenophora teres (barley helmintosporiosis):
  • aqueous suspension of the active material to be tested having the following composition is prepared by fine grinding: - active ingredient: 60 mg
  • This aqueous suspension is then diluted with water so as to obtain the desired concentration in ppm (parts per million).
  • Barley in pots, sown on a 50/50 peat earth peat substrate and maintained at 12 ° C. is treated at the 1 leaf stage (10 cm in height) by spraying the above aqueous suspension.
  • Plants, used as controls are treated with an aqueous solution not containing the active ingredient.
  • each plant is contaminated by spraying with an aqueous suspension of spores (12,000 spores per cm ⁇ ) of Pyrenophora teres. This suspension is obtained from contaminated plants.
  • the contaminated barley plants are then incubated for 24 hours at approximately 20 ° C, in an atmosphere saturated with humidity and then for seven to fourteen days at 80% relative humidity.
  • the reading is between the 8 th and 15 th day after the contamination, in comparison with the control plants.

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EP97943949A 1996-10-09 1997-10-06 Fungizide mit hydroximsäuregruppen und hydrazongruppen Withdrawn EP1021399A2 (de)

Applications Claiming Priority (3)

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FR9612524 1996-10-09
FR9612524A FR2754254B1 (fr) 1996-10-09 1996-10-09 Fongicides a groupes hydroximiques et hydrazoniques
PCT/FR1997/001774 WO1998015512A2 (fr) 1996-10-09 1997-10-06 Fongicides a groupes hydroximiques et hydrazoniques

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FR (1) FR2754254B1 (de)
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WO2000007999A1 (en) 1998-08-03 2000-02-17 Sumitomo Chemical Company, Limited Triazolone derivatives, use thereof, and intermediate therefor
CN110818596A (zh) * 2019-11-18 2020-02-21 合肥锦绣田园化工科技有限公司 一种氨基脲类化合物及其制备与应用

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PL333183A1 (en) 1999-11-22
WO1998015512A3 (fr) 1998-07-16
HUP0000194A3 (en) 2001-01-29
JP2001501943A (ja) 2001-02-13
BR9712223A (pt) 2000-05-09
IL129331A0 (en) 2000-02-17
KR20000049024A (ko) 2000-07-25
FR2754254B1 (fr) 1998-10-30
WO1998015512A2 (fr) 1998-04-16
HUP0000194A2 (hu) 2000-06-28
AU4560897A (en) 1998-05-05
AU719443B2 (en) 2000-05-11
TR199900768T2 (xx) 1999-08-23
FR2754254A1 (fr) 1998-04-10
SK45699A3 (en) 2000-01-18
EA199900346A1 (ru) 2000-02-28
CZ121499A3 (cs) 1999-08-11
CA2268021A1 (fr) 1998-04-16

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