WO1999051579A1 - Composes fongicides comportant un groupe hydroximique ou hydrazonique - Google Patents

Composes fongicides comportant un groupe hydroximique ou hydrazonique Download PDF

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WO1999051579A1
WO1999051579A1 PCT/FR1999/000753 FR9900753W WO9951579A1 WO 1999051579 A1 WO1999051579 A1 WO 1999051579A1 FR 9900753 W FR9900753 W FR 9900753W WO 9951579 A1 WO9951579 A1 WO 9951579A1
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group
formula
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PCT/FR1999/000753
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English (en)
French (fr)
Inventor
Philippe Desbordes
Charles Ellwood
Vincent Gerusz
Benoît HARTMANN
Joseph Perez
Alain Villier
Jean-Pierre Vors
Nobumitsu Sawai
Tadashi Sakurai
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Aventis Cropscience S.A.
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Priority to FR9804594A priority Critical patent/FR2777002A1/fr
Priority claimed from FR9804594A external-priority patent/FR2777002A1/fr
Application filed by Aventis Cropscience S.A. filed Critical Aventis Cropscience S.A.
Priority to CA002324940A priority patent/CA2324940A1/fr
Priority to BR9909600-5A priority patent/BR9909600A/pt
Priority to IL13890599A priority patent/IL138905A0/xx
Priority to JP2000542300A priority patent/JP2002510678A/ja
Priority to EP99911852A priority patent/EP1070052A1/fr
Priority to AU30392/99A priority patent/AU3039299A/en
Publication of WO1999051579A1 publication Critical patent/WO1999051579A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D215/14—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom 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
    • C07D333/28—Halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Definitions

  • the present invention relates to new compounds comprising a hydroximic or hydrazonic function, their method of preparation, their use as fungicides, in particular in the form of fungicidal compositions, and the methods of controlling phytopathogenic fungi in crops using these compounds or these compositions.
  • patent applications EP-A-0463488 and EP-A-370629 describe in particular fungicidal compounds comprising a hydroximic or hydrazonic function.
  • EP-A-0299694, WO-A-96/33164 and JP-09031048 also describe similar fungicidal compounds.
  • the known fungicidal compounds are weakly active and / or have a relatively narrow spectrum of activity.
  • the user In order to eradicate all the different species of fungi attacking plants, the user must for example use several products, of which he must know exactly the spectrum and the doses of application. The use of several products goes against the methods of treatment of crops recommended today, where the application doses must be as low as possible, with the obvious aim of protecting the environment.
  • An object of the present invention is to provide a new family of compounds having a broad spectrum of action on phytopathogenic fungi in crops.
  • Another object of the present invention is to propose a new family of compounds having a broad spectrum of action on phytopathogenic fungi of cultures making it possible to solve the specific problems encountered.
  • Another object of the present invention is to provide a new family of compounds having a broad spectrum of improved action on phytopathogenic fungi of crops such as cereals, rice, fruit trees, forest trees, vines, oil crops , vegetable crops, solaneas and beets.
  • the invention relates to compounds comprising a heterocyclic motif A associated with a hydroximic or hydrazonic function, of general formula (I):
  • n 0 or 1
  • Q is the nitrogen atom or the CH group
  • Q 2 is the oxygen or sulfur atom
  • Q 3 is the oxygen or sulfur atom
  • Q 4 is the nitrogen atom or the group CR
  • Q 5 is the oxygen, sulfur atom or the group NR 12 ,
  • Y is the oxygen, sulfur or amino (NH) or oxyamino group
  • W is the oxygen or sulfur atom or the sulfinyl (SO) or sulfonyl (SO 2 ) groups
  • W 2 is the oxygen atom or the NR 13 group
  • p represents 0, 1 or 2
  • A represents an aromatic heterocyclic radical, mono or bicyclic, comprising from 5 to 10 atoms, among which 1 to 4 are heteroatoms chosen from oxygen, sulfur or nitrogen atoms, each sulfur atom or - 4 -
  • X ,, X 2 , X 3 , X 4 and X 5 are independently of each other a hydrogen atom, a halogen atom; or a hydroxy, mercapto, nitro, thiocyanato, azido, cyano or pentafluorosulfonyl group; or a lower alkyl, lower haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyle, alkylthioalkyle, haloalkylthioalkyle, cyanoalkyle, cyanoalkoxy, cyanoalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonylonylsulfonylonylsulfonylonyl or a lower cycloalkyl, lower halocycloalkyl,
  • X 6 is a hydrogen atom, a halogen atom; or a lower alkyl, lower haloalkyl, alkoxy, haloalkoxy group; or the cyano, nitro,
  • R 1 and R 2 are, independently of one another, a hydrogen atom, a lower alkyl group, lower haloalkyl, a lower cycloalkyl group, lower halocycloalkyl, an alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl group; or - 5 -
  • R, and R 2 may together form a divalent radical such as an alkylene group, optionally substituted by one or more halogen atoms, optionally substituted by one or more lower alkyl groups,
  • R 3 is hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl; or a nitro, cyano, acyl, carboxy, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, lower alkoxycarbonyl, 3-oxetanyloxycarbonyl, alkylthiocarbonyl, haloalkoxy-carbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiocarbon group; or an alkenyl, alkynyl, N, N-dialkylamino, N, N-dialky
  • R 4 is lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl; or an alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino group,
  • R 5 and Rg represent, independently of one another, a lower alkyl or lower haloalkyl group
  • R 7 is a lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl group,
  • R 8 is a lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl, formyl, acyl group, Rg is hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl,
  • R 10 is a halogen atom, a lower alkyl group, lower haloalkyl, a lower cycloalkyl group, lower halocycloalkyl, an alkoxy group, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl,
  • R ⁇ and R 12 are independently of each other hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl,
  • R 13 is hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, optionally substituted allyl group, optionally substituted propargyl group, optionally benzyl group 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,
  • Q 2 and R 4 can together form a ring of 5 to 7 atoms containing 2 to 3 atoms of oxygen and / or nitrogen, optionally substituted by one or more radicals such as a halogen, a lower alkyl or lower haloalkyl group,
  • this compound may be capable of admitting a tautomeric form in chemical equilibrium, resulting from the displacement of the proton of said hydroxy, mercapto, amino, N-alkylamino or N-acylamino group.
  • the tautomeric forms of such compounds are included in the scope of the invention.
  • Such tautomeric forms are in particular defined in the work "The tautomerism of heterocycles, Advances in Heterocyclic Chemistry, Supplement 1" by J. Elguero, C. Martin, AR Katritzky and P. Linda, published by Académie Press, New York, 1976, pages 1-4.
  • 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, the exception of the cycloalkyl radical where the adjective "lower” means from 3 to 6 carbon atoms,
  • alkyl radicals can be linear or branched
  • halogenated alkyl radicals may contain one or more identical or different halogen atoms
  • acyl radical signifies alkylcarbonyl, or cycloalkylcarbonyl, - 8 -
  • 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:
  • W is the oxygen or sulfur atom
  • W 2 is the oxygen atom or an alkylamino, haloalkylamino, alkoxyalkylamino, allylamino group
  • Y is the oxygen atom
  • X ,, X 2 , X 3 , X 4 , X 5 and X 6 are independently of each other a hydrogen atom, a lower alkyl group, a halogen atom, or the cyano, trifluoromethyl, methoxy, nitro radicals ,
  • R 1 and R 2 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, or N, N-dialkylcarbamoyl,
  • R 3 is a hydrogen atom, a lower alkyl, lower cycloalkyl, lower haloalkyl, alkoxyalkyl group, preferably a methyl, ethyl, propyl, isopropyl, cyclopropyl or methoxymethyl radical,
  • R 4 is a lower alkyl, alkoxy, alkylamino, dialkylamino group, preferably a methyl, ethyl, propyl, methoxy, ethoxy, methylamino or ethylamino radical, - 9 -
  • R 5 , R ⁇ , R 8 and R are independently of each other a lower alkyl group, lower haloalkyl, preferably a methyl, fluoromethyl, difluoromethyl, trifiuoromethyl, ethyl, 2,2,2-trifluoroethyl, or propyl radical,
  • R 7 is a lower alkyl, lower haloalkyl group, preferably a methyl, fluoromethyl, difluoromethyl, trifiuoromethyl, ethyl, 2,2,2-trifluoroethyl, propyl, an allyl or propargyl group,
  • R 10 is a chlorine atom, a lower alkyl group, lower haloalkyl, preferably methyl, an alkoxy, alkylthio, preferably methoxy, or methylthio group
  • R ⁇ and R 12 are independently of each other an alkyl group lower, lower haloalkyl, alkoxyalkyl, allyl, propargyl,
  • R 13 is the hydrogen atom, a lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, allyl, propargyl, benzyl,
  • A is chosen from a radical, optionally substituted by 1 to 5 radicals X, and / or X 2 and / or X 3 and / or X 4 and / X 5 , preferably by 1 to 3 radicals X, and / or X 2 and / or X 3 , derived, by elimination of a hydrogen atom, from one of the following cycles (i) to (v):
  • each of the groups in the list B ⁇ , B ⁇ , B ⁇ , B ⁇ , B ⁇ , is chosen from carbon, nitrogen, oxygen and sulfur atoms such that the said list has 0 to 3 carbon atoms, has 0 to 1 sulfur atom, 0 to 1 oxygen atom and 0 to 4 nitrogen atoms; or else - a 6-link cycle described by formula (ii):
  • each of the groups in the list D, D ⁇ , D ⁇ , D ⁇ , D ⁇ , D ⁇ , is chosen from carbon or nitrogen atoms such that said list comprises from 1 to 4 carbon atoms and from 1 to 4 nitrogen atoms; or, - two cycles merged with 6 links each, described by formula (iii): - 10 -
  • each of the groups in the list E ⁇ , E ⁇ , E ⁇ , E ⁇ , E ⁇ , E ⁇ E ?, E ⁇ is chosen from carbon or nitrogen atoms such that said list contains from 4 to 7 carbon atoms and from 1 to 4 nitrogen atoms; or
  • each of the groups in the list jl, fi, ⁇ , ⁇ ,, ⁇ is chosen from carbon or nitrogen atoms such that said list comprises from 3 to 6 carbon atoms, and from 0 to 3 d atoms 'nitrogen;
  • each of the groups in the list L 1 , ifi, ⁇ is chosen from carbon, nitrogen, oxygen or sulfur atoms such that said list comprises from 0 to 3 carbon atoms, from 0 to 1 sulfur atom, 0 to 1 oxygen atom and 0 to 3 nitrogen atoms;
  • each of the groups in the list ⁇ , fi, fi,, ⁇ ,, i, ⁇ fi, ⁇ ⁇ is chosen so that said list contains from 3 to 8 carbon atoms;
  • each of the groups in the list M, M ⁇ represents the carbon, nitrogen, oxygen or sulfur atoms such that the said list comprises from 0 to 3 carbon atoms, from 0 to 1 atom sulfur, from 0 to 1 oxygen atom and from 0 to 3 nitrogen atoms; - 77 -
  • each of the groups in the list T ⁇ , T ⁇ , T ⁇ represent the carbon, nitrogen, oxygen or sulfur atoms such that the said list comprises from 0 to 3 carbon atoms, from 0 to 1 sulfur atom, 0 to 1 oxygen atom and 0 to 3 nitrogen atoms;
  • - Z represents the carbon or nitrogen atom;
  • each of the groups in the list M *, M ⁇ , M ⁇ , ⁇ l, T ⁇ , T ⁇ es t chosen so that said list contains from 0 to 6 carbon atoms.
  • W is the oxygen atom
  • R is the hydrogen atom or the methyl radical
  • R 2 is the hydrogen atom or a lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N, N-dialkylaminoalkyl, lower alkoxycarbonyl, N, N-dialkyl- group lower carbamoyl,
  • A represents a heterocyclic radical, optionally substituted by 1 to 5 radicals X, and / or X 2 and / or X 3 and or X 4 and / or X 5 , preferably by 1 to 3 radicals X, and / or X 2 and / or X 3 as defined above, A being chosen from the following list:
  • pyrimidinyl pyrazinyl; pyridazinyl; 1,2,3-triazinyl; 1,2,4-triazinyl; 1,3,5-triazinyl; 1,2,3,4-tetrazinyl; 1,2,3,5-tetrazinyl; 1,2,4,5-tetrazinyl;
  • 1,2-benzisothiazolyl 2,1-benzisothiazolyl; 1,2,3-benzoxadiazolyl; 1,2,5-benzoxadiazolyle; 1,2,3-benzothiadiazolyl; 1,2,5-benzothiadiazolyle;
  • W is the oxygen atom
  • R is the hydrogen atom or the methyl radical
  • R 2 is a hydrogen atom or a lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N, N-dialkylaminoalkyl, lower alkoxycarbonyl, N, N-dialkyl-carbamoyl group, in which A, optionally substituted with 1 to 5 radicals X ) and or X 2 and / or X 3 and / or X 4 and / or X 5 , preferably by 1 to 3 radicals X, and / or X 2 and / or X 3 , is chosen from one of the heterocycles following:
  • - pyridazinyl pyrimidinyl; pyrazinyl; 1,3,5-triazinyl; 1,2,4-triazinyl; - quinolinyl; isoquinolinyl;
  • W is the oxygen atom
  • R is the hydrogen atom or the methyl radical
  • R 2 is the atom hydrogen or lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N, N-dialkylaminoalkyl, lower alkoxycarbonyl, N, N-dialkyl-carbamoyl, in which A, optionally substituted by 1 to 5 radicals X, and / or X 2 and / or X 3 and / or X 4 and / or X 5 , preferably by 1 to 3 radicals X, and / or X 2 and / or X 3 , represents the pyridinyl radical.
  • 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 according to the number of double bonds of the - 14 -
  • the compounds of general formula (I) where G is the group Gl, G2 or G3 can comprise four different geometric isomers denoted (E, E), (E, Z), (Z, E), (Z, Z) according to 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.
  • the compounds of general formula (I) where G is the group G4 to G9 can comprise two different geometric isomers denoted (E) or (Z) according to 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 optical isomers as well as their racemic or scalemic mixtures (scalemic is a mixture of enantiomers in different proportions), as well as mixtures of all possible stereoisomers in all proportions.
  • 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 K.
  • 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), X 6 having the same definition as that indicated for the formula (I), V, is a halogen atom (preferably chlorine or bromine), an alkylsulfonate or haloalkylsulfonate group (preferably methylsulfonate or trifiuoromé hylsulfonate), arylsulfonate (preferably 4-methylphenylsulfonate),
  • reaction 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 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, di-isopropyl 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, dime hylprolylene-urea, dimethylsulfox
  • organic or inorganic base suitable for this reaction mention may be made of the hydroxides of alkali and alkaline-earth metals such as sodium, potassium, cesium or calcium hydroxide; alkali and alkaline earth metal alcoholates such as potassium tert-butoxide, alkali and alkaline earth metal hydrides such as sodium, potassium or cesium hydride; carbonates and bicarbonates of alkali and alkaline earth metals 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 di-isopropylethylamine, aza derivatives such as 1,5-diazabicyclo [4.3.0] non-5-ene or 1,8-diazabicyclo [5.4.0] undec-7-ene.
  • alkali and alkaline earth metal alcoholates such as potassium tert-butoxide
  • 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 group configuration - 17 -
  • hydroximic or hydrazonic hydroximic or hydrazonic. 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.
  • Ui is a halogen atom (preferably chlorine or bromine), or a hydroxy, lower alkoxy or benzyloxy, lower alkylthio, amino, N radical.
  • -alkylamino, N, N-dialkylamino, N-acylamino, N, N-acylalkylamino or the group -O (C O) R a , R, having the same definition as that of R 3 indicated for formula (I) and being identical to R 3 or different, U, preferably being a halogen atom, the compound of formula (V) then representing an acid halide.
  • Condensation between the compound of formula (IV) and compound of formula (V) is generally carried out in the presence of an organic or inorganic base, or of a dehydration reagent such as anhydrides of carboxylic acids, preferably anhydride acetic acid or propionic anhydride, in the absence or presence of a solvent.
  • a dehydration reagent such as anhydrides of carboxylic acids, preferably anhydride acetic acid or propionic anhydride
  • Derivatives of hydroxamic acids or hydrazonic acids of formula (III) A where W, is the oxygen atom, W 2 , R ,, R 2 , R 3 , p and A having the same definition as that indicated for formula (I), can also be obtained by a process comprising bringing a compound of formula (VI) into contact:
  • (I), and V ! is a halogen atom (preferably chlorine or bromine), an alkylsulfonate or haloalkylsulfonate group (preferably methylsulfonate or trifiuoromethylsulfonate), or arylsulfonate (preferably 4-methylphenylsulfonate), with a hydroxamic acid or hydrazonic acid derivative, W 2 and R 3 having the same definition as that indicated for formula (I), of formula (VII):
  • the condensation between the compound of formula (VI) and the compound of formula (VII) is generally carried out in the presence of an organic or inorganic base, in the absence or in the presence of a solvent.
  • the general conditions of condensation between the compound of formula (VI) and the compound of formula (VII) are similar or identical to the conditions of condensation between the compound of formula (II) A and the compound of formula (III) A and are known per se according to "Houben-Weyl" volume E5, pages 1148-1149.
  • the condensation between the compound of formula (VII), W 2 being the oxygen atom, R 3 having the same definition as that indicated for formula (I), and the compound of formula (VIII), R StammR 2 and A having the same definition as that indicated for formula (I), is generally carried out in the presence of a coupling agent such as carbodi-imides or bis-alkoxycarbonylazoic or bis- (N, N-dialkyl) carbamoylazo derivatives of preferably diethyl azodicarboxylate and a trialkylphosphine or triarylphosphine, preferably triphenylphosphine, in the absence or in the presence of an aprotic solvent, such as ethers, in particular diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane ; such as halogenated hydrocarbons, in particular dichloromethane, chloroform, 1, 2-dichloroethane, 1,1,1
  • the reaction is generally carried out at a temperature between -80 ° C and 120 ° C (preferably between 0 ° C and 60 ° C) or at the boiling point of the solvent used.
  • the reaction time depends on the conditions used and is generally between 0.1 to 48 h.
  • the compounds of formula (IV), formula (V), formula (VI), formula (VII) and formula (VIII), W ,, W 2 , R ,, R 2 , R 3 , p and A having the same definition that that indicated for formula (I), U, and V, having the same definition as that indicated in method A can be prepared according to methods known per se, for example Tetrahedron (1995), 5J., 11473 and Tetrahedron Lett. (1996), 37, 8045 for the compounds of formula (IV) and Synthesis (1980), 746 for the compounds of formula (VI).
  • the compounds of formula (VI) and of formula (VIII) can be more particularly prepared according to very numerous methods known per se and described in "The chemistry of heterocyclic compounds” volumes 1 to 52, Ed.
  • G9 the groups Gl to G9 having the same definition as that indicated for the formula (I), X 6 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 trifluoromethylsulfonate), arylsulfonate (preferably 4-methylphenylsulfonate), will be by convention, for the description of the preparation methods, designated by the generic term of "halide derivatives of benzyles ".
  • halogen atom preferably chlorine or bromine
  • an alkylsulfonate group preferably methylsulfonate or trifluoromethylsulfonate
  • arylsulfonate preferably 4-methylphenylsulfonate
  • benzyl halide derivatives of formula (II) A where V, is a halogen atom (preferably chlorine or bromine) can be obtained by halogenation of a compound of formula (IX):
  • G is one of the groups Gl to G9, the groups Gl to G9 having the same definition as that indicated for the formula (I), X 6 having the same definition as that indicated for the formula (I).
  • halogenation of the compound of formula (IX) can be carried out by radical, thermal or photochemical route, the various processes not being - 21 -
  • N-haloacetamide such as N-bromosuccinimide, N-chlorosuccinimide, N-bromoacetamide
  • an inert solvent such as benzene or carbon tetrachloride or in the absence of solvent with or without a free radical initiator at a temperature of 20 ° C to 170 ° C preferably from 80 ° C to 100 ° C according to J. March ibid. pages 689-697.
  • 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 R 4 is the group alkylamino, dialkylamino, the groups G8 and G9 having the same definition that that indicated for formula (I), X 6 having the same definition as that indicated for formula (I), W, is the oxygen atom, with a halogenating agent such as thionyl chloride, the 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, the 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 V, is a halogen atom (preferably chlorine or bromine) can also be obtained by cutting a compound of formula (II) C:
  • G is one of the groups Gl to G9, the groups Gl to G7 having the same definition as that indicated for the formula (I) and R 4 is the group - 22 -
  • benzyl halide derivatives of formula (II) A and the compounds of formula (IX), (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 method K.
  • Gl to G9 the groups Gl to G7 having the same definition as that indicated for the formula (I) and R 4 is the group or radical amino, alkylamino, dialkylamino, the groups G8 and G9 having the same definition as that indicated for the formula (I), X 6 having the same definition as that indicated for formula (I), can be obtained by a process comprising bringing a compound of formula (II) B into contact in which G is one of the groups Gl to G9, the groups Gl to G7 having the same definition as that indicated for the formula (I) and R 4 is the amino or alkylamino, dialkylamino group or radical, the groups G8 and G9 having the same definition as that indicated for formula (I), X 6 having the same definition as that indicated for formula (I), and Wl is the oxygen or sulfur atom,
  • This reaction is generally 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 dimethyl sulfoxide. 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 hy
  • 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- potassium butylate.
  • 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. 24
  • the compounds of general formula (III) B are prepared according to methods known per se, for example, J. Org. Chem. (1985), 50, 993, J. Org. Chem. (1971X36, 234, and Chem. Abstracts (1970), 73, 34750s.
  • the thiohydroxamic acid derivatives of formula (III) A where W, is the sulfur atom and W 2 is the oxygen atom or the thiohydrazonic acid derivatives of formula (III) A where W, is the sulfur atom and W 2 is the group NR 13 , R réelleR 2 , R 3 , R 13 , p and A having the same definition as that indicated for formula (I), are also the object of the present invention.
  • R 4 is the alkoxy, alkylamino, dialkylamino group, the other substituents having the same definition as that indicated for formula (I),
  • Rg being a lower alkyl or lower haloalkyl group
  • R b being a lower alkyl, phenyl or benzyl group
  • R é being a lower alkyl or lower haloalkyl group
  • R d being an optionally substituted phenyl group
  • a base such as the alkali metal
  • the Wittig-Horner reagents of formula (XI) A and the Wittig reagents of formula (XI) B can be obtained according to methods known per se.
  • T is the oxygen or sulfur atom
  • M an alkaline or alkaline earth ion
  • Ql being the nitrogen atom or the CH group
  • T is the oxygen atom and M an alkaline or alkaline-earth ion, Q, being the group CH, R 4 being the group 27 -
  • alkoxy, alkylamino, dialkylamino, W ,, W 2 , R réelleR 2 , R 3 , X 6 , p and A having the same definition as that indicated for formula (I) can in particular be prepared in a manner similar to the patent EP-A-0178826.
  • R 4 is the alkoxy, alkylamino, dialkylamino group, the other substituents having the same definition as that indicated for formula (I), with a reagent of formula (XIV):
  • V l is a halogen atom (preferably chlorine or bromine)
  • R 5 having the same definition as that indicated for formula (I), by the action of one or more base equivalents such as alkali or alkaline earth metal hydroxides, 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 a quaternary ammonium, in an aprotic solvent such as ethers preferably diethyl ether or tetrahydrofuran at a temperature of -78 ° C to 40 ° C preferably between -20 and 25 ° C. - 28 -
  • a phase transfer catalyst such as a quaternary ammonium
  • R 4 is the alkoxy, alkylamino, dialkylamino, X 6 group having the same definition as that indicated for formula (I),
  • V 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 G1 to G7 and R 4 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 comprising contacting a compound of general formula (I) for which G is the group G1 to G7 and R 4 is the alkoxy or alkylthio group, the other substituents having the same definition as that indicated for the formula (I) , - 29 -
  • alkylamine or dialkylamine preferably methylamine
  • an alcoholic solvent such as methanol, ethanol, propanol or isopropanol
  • G is one of the groups Gl to G9, the groups Gl to G9 having the same definition as that indicated for the formula (I), X 6 , W ,, W 2 and R 3 having the same definition as those indicated for formula (I),
  • a compound of formula (VI), R réelleR 2 , p and A having the same definition as that indicated for formula (I), and V is a halogen atom (preferably chlorine or bromine), a group alkylsulfonate or haloalkylsulfonate (preferably methylsulfonate or trifluoromethylsulfonate), an arylsulfonate group (preferably 4-methyl ⁇ henylsulfonate).
  • the condensation between the compound of formula (XV) A and the compound of formula (VI) is generally 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 those indicated for the formula (I), X 6 , W ,, W 2 and R 3 having the same definition as those indicated for formula (I), and P is a protecting group for the hydroxyl function such as an ester preferably acetic or benzoic, a silylated ether such as the trialkylsilyl ether, the - 31 -
  • W ,, W 2 and R 3 having the same definition as those indicated for formula (I) and P being a protecting group for the hydroxyl function or a protecting group for the amino function.
  • the condensation between the compound of formula (II) A and the compound of formula (XVI) is generally carried out in the presence of an organic or inorganic base, in the absence or in the presence of a solvent.
  • W 2 having the same definition as those indicated for formula (I) and P being a protecting group for the hydroxyl function or a protecting group for the amino function
  • W ,, R 3 having the same definition as that indicated for formula (I), U
  • is a halogen atom (preferably chlorine or bromine), or a hydroxy, lower alkoxy or benzyloxy, lower alkylthio, amino, N-alkylamino, N, N radical -dialkylamino, N-acylamino, N, N-acylalkylamino or the group -O (C O) R a , R a having the same definition as that of R 3 indicated for formula (I) and being identical to R 3 or different, U, preferably being a halogen atom, the compound of formula (V) then representing an acid halide.
  • the compounds of formula (XVII) can be prepared according to methods known per se.
  • the reaction time is chosen so as to obtain a total conversion of the cis isomer to 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, trifluoromethanesulfonic, 4-methylphenylsulphonic or sulfuric acid.
  • benzyl halide derivatives of formula (II) A and the compounds of formula (IX), (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 what is described in patents EP-A-0426460 , EP-A-0398692, EP-A-0617014, EP-A-0585751, EP-A-0487409, EP-A-0535928, DE-4305502,
  • the benzyl halide derivatives of formula (II) A and the like, where G is the group G1 or G2 of stereochemistry (E) or (Z) and Q 2 and R 4 together form a ring of 5 to 7 atoms containing 2 with 3 oxygen and / or nitrogen atoms, are known according to patent WO-A-95/04728,
  • the benzyl halide derivatives of formula (II) A and the like, where G is the group G3 of stereochemistry (E) or (Z) are known according to patent WO 9616943,
  • the invention also relates to fungicidal compositions comprising an effective amount of at least one active material of formula (I).
  • the compounds of formula (I) according to the invention are fungicidal compounds active on a very wide range of phytopathogenic fungi in crops. - 35 -
  • these compounds of formula (I) are not or very weakly phytotoxic. That is to say that they have a very good selectivity with respect to the fungi to be combated.
  • the fungicidal compositions according to the invention comprise a compound of formula (I) or a salt thereof acceptable in agriculture or a metallic or metalloid complex of this compound, in combination with a solid or liquid support, acceptable in agriculture and / or an agent surfactant also acceptable in agriculture.
  • a solid or liquid support acceptable in agriculture and / or an agent surfactant also acceptable in agriculture.
  • the usual inert supports and the usual surfactants can be used.
  • 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. Mention may be made, for example, of salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulfonic or naphthalene sulfonic acids, polycondensates of ethylene oxide on fatty alcohols or on fatty acids or on fatty amines , substituted phenols (in particular alkylphenols or arylphenols), ester salts of sulfosuccinic acids, taurine derivatives (in particular alkyltaurates), phosphoric esters of polyoxyethylated alcohols or phenols, esters of acids fatty acids and polyols, the derivatives containing sulfates, sulfonates and phosphates of the preceding compounds.
  • the presence of at least one surfactant is generally essential when the active material and / or the
  • 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.
  • water-soluble concentrates 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 sparingly or not very soluble: certain organic solids or mineral salts can be dissolved in the support to help prevent sedimentation or as antifreeze for water.
  • 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 ingredients are intimately mixed in the appropriate mixers with the additional substances and ground with mills or other suitable grinders. This gives spray powders whose wettability and - 38 -
  • suspensions are advantageous; they can be suspended with water at any desired concentration and these suspensions can be used very advantageously in particular for application for example on the leaves of plants or on seeds.
  • compositions of wettable powders As an example, here are various compositions of wettable powders (or spraying powders):
  • Example PM 1 active ingredient 50%
  • 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".
  • 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 90%, 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, for example, constituted by at least one dispersing agent, essentially anionic, such as a polynaphthalene alkaline or alkaline earth sulfonate or an alkaline or alkaline earth lignosulfonate, the remainder being nonionic or anionic wetting agents such as an alkali or alkaline earth alkyl naphthalene sulfonate.
  • dispersing agent essentially anionic, such as a polynaphthalene alkaline or alkaline earth sulfonate or an alkaline or alkaline earth lignosulfonate, the remainder being nonionic or anionic wetting agents such as an alkali or alkaline earth alkyl naphthalene sulfonate.
  • 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.
  • 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 In a mixer, the following constituents are mixed: - active material 75%
  • This mixture is granulated in a fluid bed, in the presence of water, then dried, crushed and sieved so as to obtain granules of size between 0.15 and
  • 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, acaricides, arthropodicides, nematocides, attractants or pheromones or other compounds with biological activity. - 41 -
  • mixtures thus obtained have a broad spectrum activity.
  • Mixtures with other fungicides are particularly advantageous, for example mixtures with carbendazim, thiram, diethofencarb, dodine, maneb, mancozeb, diflumetorim, ethirimol, benomyl, cymoxanil, fenpropidine, fenpropimorph, triadimefon, captan, captafol, folpel, thiophanate, thiabendazole, phosphoric acid and its derivatives such as phosetyl-Al, chlorothalonil, copper fungicidal compositions, dichloran, metalaxyl , iprodione, fenamidone, oxadixyl, vinchlozoline, tebuconazole, bromuconazole, triticonazole, difenconazole, diniconazole, metconazole, penconazole, prop
  • compositions according to the invention are also useful for treating seeds, for example cereals (wheat, rye, triticale and barley in particular), potato, cotton, peas, rapeseed, corn, flax or else 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 of combating, for curative or preventive purposes, phytopathogenic fungi in crops, characterized in that the seeds, leaves or trunks of plants or the soils where these plants grow or are liable to grow. plants are treated by application, spraying or - 42 -
  • 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.
  • multiplication products of the plants concerned mention may in particular be made of seeds or seeds, and tubers.
  • compositions according to the invention can also be applied as a foliar application to plant crops.
  • plants targeted by the method according to the invention there may be mentioned as non-limiting examples:
  • foot rot Pseudocercosporella herpotricho ⁇ des
  • foot scald Gaeumannomyces graminis
  • fusarium wilt F. culmorum, F. graminearum
  • rhizoctonia Rhizoctonia cerealis
  • powdery mildew Erysiphe graminis forma specie tritici
  • rusts Puccinia striiformis and Puccinia recondita
  • septoria Septoria tritici and Septoria nodorum
  • helminthosporioses Pyrenophora graminea, Pyrenophora ter es and
  • Cochliobolus sativus Cochliobolus sativus
  • anthrax Ustilago nuda
  • fusarium wilt Mochliobolus sativus
  • anthrax Ustilago nuda
  • fusarium wilt Macrodochium nivale and Fusarium roseum
  • foot rot Pseudocercosporella herpotricho ⁇ des
  • helminthosporioses Pyrenophora ter es and Cochliobolus sativus
  • powdery mildew Erysiphe graminis forma specie hordei
  • dwarf rust Puccinia hordei
  • rhynchosporiosis Rhynchosporium secalis
  • the potato as regards the fight against the diseases of the tuber (in particular Helminthosporium solani, Phoma tuberosa, Rhizoctonia solani, Fusarium solani) and certain viroses (virus Y);
  • diseases of the tuber in particular Helminthosporium solani, Phoma tuberosa, Rhizoctonia solani, Fusarium solani
  • viroses virus Y
  • 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.
  • Step 1 Preparation of N - [(5-chloro-2-thiophenyl) methoxy] acetamide
  • Step 1 Preparation of N - [(3,5-dimethyl-4-isoxazolyl) -methoxy] cyclopropane-carboxamide
  • Methyl (E, E) -2- (2- ⁇ 1 - [(3, 5-dimethyl-4-isoxazolyl) methyloxyimino] - 1-cyclopro-pylmethyloxymethyl ⁇ phenyl) -2-methoxyiminoethanoate is prepared according to a similar procedure to that given in Example 3, step 2.
  • Step 1
  • N-hydroxyphthalimide and 12.8 g of potassium carbonate in 280 ml of dimethylformamide is stirred at 80 ° C for 7 h.
  • the crude reaction product is partitioned between an aqueous phase and ethyl acetate.
  • the aqueous phase is extracted with ethyl acetate, the organic phases are combined and washed with a saturated aqueous solution of sodium chloride, then dried and evaporated.
  • the solid obtained is recrystallized from di-isopropyl ether, which gives 11.52 g of N- [1- (2-pyridinyl) propyloxy] phthalimide in the form of a white solid. Mp 123 ° C.
  • Step 1
  • Step 2 Preparation of N- [1 - (6-methyl-2-pyridinyl) ethyloxy] phthaIimide
  • Step 4 Preparation of N- [1- (6-methyl-2-pyridinyl) ethoxy] cyclopropanecarboxamide
  • Step 1
  • a mixture of 14 g of methyl 2- (6-methyl-3-pyridinyl) propionate, 14 g of N-bromosuccinimide and 1 g of benzoyl peroxide in 300 ml of carbon tetrachloride is stirred for 3 h under lighting halogen lamp. After filtration, the organic solution is washed with a saturated aqueous solution of sodium chloride, then with a saturated aqueous solution of sodium thiosulfate, and again with a saturated aqueous solution of sodium chloride, dried and evaporated.
  • Step 1
  • Step 3 Preparation of (E, E) -2- (2- ⁇ l- [1- (4-quinolyl) ethyloxyimino] ethyloxy-methyl ⁇ -phenyl) -2-methoxyiminoethanoate
  • Step 1 Preparation of N- [2 (-2-pyridinyl) ethoxy] phthalimide
  • Step 2 Preparation of (E, E) -2- (2- ⁇ l- [2- (2-pyridinyl) ethoxyimino] -l-cyclopropyl- methyloxymethyl ⁇ pheny l) -3-methyl methoxypropenoate 56
  • Pr means n-propyl
  • cPr means cyclopropyl
  • R 5 Me; R ⁇ OMe 57 -

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mycology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microbiology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
  • Quinoline Compounds (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)
  • Pyridine Compounds (AREA)
PCT/FR1999/000753 1998-04-07 1999-04-01 Composes fongicides comportant un groupe hydroximique ou hydrazonique WO1999051579A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
FR9804594A FR2777002A1 (fr) 1998-04-07 1998-04-07 Nouveaux composes fongicides
CA002324940A CA2324940A1 (fr) 1998-04-07 1999-04-01 Composes fongicides comportant un groupe hydroximique ou hydrazonique
BR9909600-5A BR9909600A (pt) 1998-04-07 1999-04-01 Compostos fungicidas comportando um grupo hidroxìmico ou hidrazÈnico, processo de tratamento a tìtulo preventivo ou curativo dos produtos de multiplicação de vegetais e processo de preparação de compostos
IL13890599A IL138905A0 (en) 1998-04-07 1999-04-01 Fungicide compositions comprising a hydroximic or hydrazonic group
JP2000542300A JP2002510678A (ja) 1998-04-07 1999-04-01 ヒドロキシム基またはヒドラゾン基を含む殺菌性化合物
EP99911852A EP1070052A1 (fr) 1998-04-07 1999-04-01 Composes fongicides comportant un groupe hydroximique ou hydrazonique
AU30392/99A AU3039299A (en) 1998-04-07 1999-04-01 Fungicide compositions comprising a hydroximic or hydrazonic group

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR98/04594 1998-04-07
FR9804594A FR2777002A1 (fr) 1998-04-07 1998-04-07 Nouveaux composes fongicides
FR98/10934 1998-08-28
FR9810934A FR2777003A1 (fr) 1998-04-07 1998-08-28 Nouveaux composes fongicides

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2798929A1 (fr) * 1999-09-28 2001-03-30 Aventis Cropscience Sa Nouveaux composes fongicides optiquement actifs
WO2001025206A1 (fr) * 1999-10-07 2001-04-12 Aventis Cropscience Sa Procede de preparation de composes hydroximiques utiles en tant que fongicides
US7662824B2 (en) 2005-03-18 2010-02-16 Janssen Pharmaceutica Nv Acylhydrazones as kinase modulators

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0299694A2 (en) * 1987-07-11 1989-01-18 AgrEvo UK Limited Acrylate fungicides
EP0370629A1 (en) * 1988-11-21 1990-05-30 Zeneca Limited Fungicides
WO1990007493A1 (de) * 1988-12-29 1990-07-12 F. Hoffmann-La Roche Ag Aldimino- oder ketimino-oxy-ortho-tolylacrylsäure-methylester, ihre herstellung und diese enthaltende fungizide
EP0463488A1 (de) * 1990-06-27 1992-01-02 BASF Aktiengesellschaft O-Benzyl-Oximether und diese Verbindungen enthaltende Pflanzenschutzmittel
WO1996033164A1 (en) * 1995-04-17 1996-10-24 Rhone-Poulenc Agrochimie New hydroximic acid derivatives
JPH0931048A (ja) * 1995-07-21 1997-02-04 Sumitomo Chem Co Ltd オキシイミノジチオカルバミン酸誘導体およびその用途

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0299694A2 (en) * 1987-07-11 1989-01-18 AgrEvo UK Limited Acrylate fungicides
EP0370629A1 (en) * 1988-11-21 1990-05-30 Zeneca Limited Fungicides
WO1990007493A1 (de) * 1988-12-29 1990-07-12 F. Hoffmann-La Roche Ag Aldimino- oder ketimino-oxy-ortho-tolylacrylsäure-methylester, ihre herstellung und diese enthaltende fungizide
EP0463488A1 (de) * 1990-06-27 1992-01-02 BASF Aktiengesellschaft O-Benzyl-Oximether und diese Verbindungen enthaltende Pflanzenschutzmittel
WO1996033164A1 (en) * 1995-04-17 1996-10-24 Rhone-Poulenc Agrochimie New hydroximic acid derivatives
JPH0931048A (ja) * 1995-07-21 1997-02-04 Sumitomo Chem Co Ltd オキシイミノジチオカルバミン酸誘導体およびその用途

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 126, no. 16, 21 April 1997, Columbus, Ohio, US; abstract no. 211913, UJIHARA K. ET AL.: "Preparation of oxyiminodithiocarbamic acid derivatives as agricultural and horticultural fungicides, insecticides and acaricides" XP002087545 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2798929A1 (fr) * 1999-09-28 2001-03-30 Aventis Cropscience Sa Nouveaux composes fongicides optiquement actifs
WO2001023355A1 (fr) * 1999-09-28 2001-04-05 Aventis Cropscience Sa Nouveaux composes fongicides optiquement actifs comportant une fonction hydroximique ou hydrazonique
WO2001025206A1 (fr) * 1999-10-07 2001-04-12 Aventis Cropscience Sa Procede de preparation de composes hydroximiques utiles en tant que fongicides
FR2799460A1 (fr) * 1999-10-07 2001-04-13 Aventis Cropscience Sa Procede de preparation de compose hydroximique
US7662824B2 (en) 2005-03-18 2010-02-16 Janssen Pharmaceutica Nv Acylhydrazones as kinase modulators

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CA2324940A1 (fr) 1999-10-14
FR2777003A1 (fr) 1999-10-01
MA24829A1 (fr) 1999-12-31
EP1070052A1 (fr) 2001-01-24
HN1999000038A (es) 2000-03-14
AR015748A1 (es) 2001-05-16
AU3039299A (en) 1999-10-25
BR9909600A (pt) 2001-09-25
IL138905A0 (en) 2001-11-25
PE20000446A1 (es) 2000-06-02
JP2002510678A (ja) 2002-04-09

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