WO1998023605A1 - Microbicides a base de derives d'acide thiophene-2-carboxylique - Google Patents

Microbicides a base de derives d'acide thiophene-2-carboxylique Download PDF

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Publication number
WO1998023605A1
WO1998023605A1 PCT/EP1997/006368 EP9706368W WO9823605A1 WO 1998023605 A1 WO1998023605 A1 WO 1998023605A1 EP 9706368 W EP9706368 W EP 9706368W WO 9823605 A1 WO9823605 A1 WO 9823605A1
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Prior art keywords
optionally substituted
formula
carbon atoms
carboxylic acid
thiophene
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PCT/EP1997/006368
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German (de)
English (en)
Inventor
Reiner Fischer
Norbert Lui
Stefan Dutzmann
Gerd Hänssler
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Bayer Aktiengesellschaft
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Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to EP97951205A priority Critical patent/EP0944615A1/fr
Priority to JP52422098A priority patent/JP2001504832A/ja
Priority to US09/308,903 priority patent/US6013664A/en
Priority to AU54824/98A priority patent/AU5482498A/en
Publication of WO1998023605A1 publication Critical patent/WO1998023605A1/fr

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    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
    • 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
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D333/40—Thiophene-2-carboxylic acid

Definitions

  • the present invention relates to new microbicidal agents based on partially known thiophene-2-carboxylic acid derivatives and the use of these substances to control undesirable microorganisms.
  • the invention also relates to new thiophene-2-carboxylic acid derivatives and a process for their preparation.
  • Control of plant diseases can be used (cf. EP-A 0 450 355 and WO 95-27 397).
  • the effectiveness of these compounds described above is not always satisfactory at low application rates.
  • R 1 represents halogen, cyano, roitro, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, phenyl or phenoxy,
  • n stands for integers from 0 to 5 and
  • R 2 for a radical of the formula -XR or stands >
  • X represents oxygen or sulfur
  • R represents hydrogen, alkyl, alkenyl, haloalkyl, alkoxyalkyl, pyran-4-yl, thiopyran-4-yl, optionally substituted cycloalkyl, optionally substituted cycloalkylalkyl, optionally substituted phenyl or optionally substituted phenylalkyl, and
  • R and R 5 independently of one another are hydrogen, alkyl, haloalkyl, alkoxyalkyl, alkenyl, alkynyl, alkoxycarbonylalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted cycloalkylalkyl, optionally substituted phenyl, optionally substituted phenylalkyl or optionally substituted heterocyclyl or
  • R 4 and R 5 together for doubly linked alkanediyl having 4 to 6
  • Carbon atoms or together represent a radical of the formula - (CH 2 ) 2 -Y- (CH 2 ) 2 -, wherein
  • Y represents oxygen, sulfur or NR 6 ,
  • R 6 represents hydrogen, alkyl having 1 to 6 carbon atoms or benzyl
  • the thiophene-2-carboxylic acid derivatives of the formula (I) which can be used according to the invention have a much better fungicidal activity than the most similarly known, prior art thiophene-carboxylic acid derivatives of the same indication.
  • Formula (I) provides a general definition of the thiophene-2-carboxylic acid derivatives which can be used according to the invention.
  • Preferred thiophene-2-carboxylic acid derivatives of the formula (I) are those in which
  • R 1 is fluorine, chlorine, bromine, nitro, cyano, straight-chain or branched alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, haloalkoxy with 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms, alkylthio with 1 to 6 carbon atoms, haloalkyl thio with 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms ,
  • n stands for the numbers 0, 1, 2, 3 or 4 and
  • R 2 for a radical of the formula
  • X represents oxygen or sulfur
  • R 3 represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, alkenyl having 2 to 6 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms, alkoxyalkyl having 1 to 6 carbon atoms in the alkoxy part and 2 to 4 carbon atoms in the alkyl part, pyran-4-yl, thiopyran-4-yl or cycloalkyl having 3 to 7 carbon atoms, which can be monosubstituted to tetrasubstituted, identical or different, by halogen and / or alkyl having 1 to 4 Carbon atoms,
  • R 3 represents cycloalkylalkyl having 3 to 7 carbon atoms in the cycloalkyl part and 1 to 4 carbon atoms in the alkyl part, where the cycloalkyl part can be mono- to tetrasubstituted, identical or different, by halogen and / or alkyl having 1 to 4 carbon atoms,
  • R represents phenyl which can be monosubstituted to trisubstituted, identical or different, by halogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, haloalkyl having 1 or 2 carbon atoms and 1 to 5 halogen atoms and / or by haloalkoxy with 1 or 2 carbon atoms and 1 to 5 halogen atoms,
  • R 3 represents phenylalkyl having 1 to 4 carbon atoms in the alkyl part, where the phenyl part can be monosubstituted to triple, identical or differently substituted by halogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, haloalkyl having 1 or 2 carbon atoms and 1 to 5 halogen atoms and / or by halogen alkoxy having 1 or 2 carbon atoms and 1 to 5 halogen atoms,
  • R 4 and R 5 independently of one another represent hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, alkyloxyalkyl having 1 to 6 carbon atoms in the alkoxy part and 1 to 4 carbon atoms in the alkyl part, alkenyl with 3 to 6 carbon atoms, alkynyl with 3 to 6 carbon atoms, alkoxycarbonylalkyl with 1 to 4 carbon atoms in the alkoxy part and 1 to 4 carbon atoms in the alkyl part, or represent cycloalkyl having 3 to 8 carbon atoms, where each of the cycloalkyl radicals can be mono- to tetrasubstituted, identical or different, by halogen and / or alkyl having 1 to 4 carbon atoms,
  • each of the cycloalkenyl radicals can be monosubstituted to tetrasubstituted, identical or different, by halogen and / or alkyl having 1 to 4 carbon atoms,
  • each of the cycloalkyl radicals can be mono- to tetrasubstituted, identical or different, by halogen and / or alkyl having 1 to 4 carbon atoms,
  • phenyl which can be monosubstituted to trisubstituted, identical or different, by halogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, haloalkyl having 1 or 2 carbon atoms and 1 to 5 halogen atoms and / or by haloalkoxy with 1 or 2 carbon atoms and 1 to 5 halogen atoms,
  • phenylalkyl having 1 to 4 carbon atoms in the alkyl part where the phenyl part can be monosubstituted to triple, identical or differently substituted by halogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, halogen alkyl with 1 or 2 carbon atoms and 1 to 5 halogen atoms and / or by haloalkoxy with 1 or 2 carbon atoms and 1 to 5 halogen atoms,
  • heterocyclyl with 5 or 6 ring members and 1 to 3 heteroatoms, such as nitrogen, oxygen and / or sulfur, it being possible for each heterocycle to be mono- or disubstituted by halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 Carbon atoms, haloalkyl having 1 or 2 carbon atoms and 1 to 5 halogen atoms and / or by haloalkoxy having 1 or 2 carbon atoms and 1 to 5 halogen atoms,
  • R 4 and R 5 together represent double-linked alkanediyl having 4 to 6 carbon atoms or together represent a radical of the formula - (CH 2 ) 2 -Y- (CH 2 ) 2 -, in which
  • Y represents oxygen, sulfur or NR 6 ,
  • R 6 represents hydrogen, alkyl having 1 to 4 carbon atoms or benzyl.
  • R 1 for fluorine, chlorine, bromine, cyano, nitro, alkyl with 1 to 4 carbon atoms, haloalkyl with 1 or 2 carbon atoms and 1 to 5 fluorine and / or chlorine atoms, alkoxy with 1 to 4 carbon atoms, haloalkoxy with 1 or 2 carbon atoms and 1 to 5 fluorine and / or chlorine atoms, alkylthio with 1 to 4 carbon atoms, haloalkylthio with 1 or 2 carbon atoms and 1 to 5 fluorine and / or chlorine atoms, phenyl or phenoxy, and
  • n represents the numbers 0, 1, 2 or 3, where R 1 can stand for the same or different radicals if n stands for 2 or 3, and
  • R 2 for a radical of the formula
  • X represents oxygen or sulfur
  • R 3 represents hydrogen, alkyl having 1 to 4 carbon atoms, alkenyl having 2 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms, alkoxyalkyl having 1 to 4 carbon atoms in the alkoxy part and 2 or 3
  • R 3 represents cycloalkylalkyl having 3 to 6 carbon atoms in the cycloalkyl part and 1 or 2 carbon atoms in the alkyl part, the
  • Cycloalkyl part can be monosubstituted to trisubstituted, identical or different, by fluorine, chlorine, bromine, methyl and / or ethyl,
  • R 3 represents phenyl, which can be monosubstituted to trisubstituted, identical or different, by fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, haloalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine - and / or chlorine atoms and / or by haloalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine and / or chlorine atoms,
  • R represents phenylalkyl with 1 or 2 carbon atoms in the alkyl part, where the phenyl part can be substituted once to three times, in the same way or differently, by fluorine, chlorine, bromine, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, haloalkyl with 1 or 2 carbon atoms and 1 to 5 fluorine and / or chlorine atoms and / or by haloalkoxy with 1 or 2 carbon atoms and 1 to 5 fluorine and / or chlorine atoms,
  • R 4 and R 5 independently of one another are hydrogen, alkyl having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 3 fluorine, chlorine and / or bromine atoms, alkoxyalkyl having 1 to 4 carbon atoms in the alkoxy part and 1 to 3 carbon atoms in the alkyl part, alkenyl with 3 to 6 carbon atoms, alkynyl with 3 to 6 carbon atoms, alkoxycarbonylalkyl with 1 or 2 carbon atoms in the alkoxy part and 1 or 2 carbon atoms in the alkyl part, or for cycloalkyl with 3 to 7 carbon atoms, each of the cycloalkyl radicals being one to four times , may be substituted identically or differently by fluorine, chlorine, bromine, methyl and / or ethyl,
  • each of the cycloalkenyl radicals can be monosubstituted to tetrasubstituted, identical or different, by fluorine, chlorine, bromine, methyl and / or ethyl,
  • each of the cycloalkyl radicals is substituted one to four times, in the same or different manner, by fluorine, chlorine, bromine, methyl and / or ethyl,
  • phenyl which can be monosubstituted to trisubstituted, identical or different, by fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, haloalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine and / or chlorine atoms and / or by haloalkoxy with 1 or 2 carbon atoms and 1 to 5 fluorine and / or chlorine atoms,
  • phenylalkyl having 1 or 2 carbon atoms in the alkyl part where the phenyl part can be substituted once to three times, identically or differently, by fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, haloalkyl having 1 or 2 Carbon atoms and 1 to 5 fluorine and / or chlorine atoms and / or by haloalkoxy with 1 or 2 carbon atoms and 1 to 5 fluorine and / or chlorine atoms,
  • heterocyclyl with 5 or 6 ring members and 1 to 3 heteroatoms, such as nitrogen, oxygen and / or sulfur, it being possible for each heterocycle to be mono- or disubstituted, identical or differently substituted by fluorine, chlorine, bromine or alkyl
  • R 4 and R 5 together represent double-linked alkanediyl having 4 to 6 carbon atoms or together represent a radical of the formula - (CH 2 ) 2 -Y- (CH 2 ) 2 -, in which
  • Y represents oxygen, sulfur or NR 6 ,
  • R 6 represents hydrogen, methyl, ethyl or benzyl
  • R 1 for fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, trifluoromethyl, methoxy, ethoxy, trifluoromethoxy, methylthio, Trifluoromethylthio, phenyl or
  • n represents the numbers 0, 1, 2 or 3, where R 1 is the same or different
  • Residues can stand if n stands for 2 or 3, and
  • R 2 for a radical of the formula
  • X represents oxygen or sulfur
  • R 3 for hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, ISO-
  • R 3 represents cycloalkylalkyl having 3 to 6 carbon atoms in the cycloalkyl part and 1 or 2 carbon atoms in the alkyl part, the
  • Cycloalkyl part can be substituted once or twice, in the same or different way, by fluorine, chlorine, bromine, methyl and / or ethyl,
  • R 3 represents phenyl which can be monosubstituted to trisubstituted, identical or different, by fluorine, chlorine, bromine, methyl, ethyl, isopropyl, tert. Butyl, methoxy, ethoxy, trifluoromethyl, and / or trifluoromethoxy,
  • R 3 represents phenylalkyl having 1 or 2 carbon atoms in the alkyl part, where the phenyl part can be substituted once to three times, in the same way or differently, by fluorine, chlorine, bromine, methyl, ethyl, isopropyl, tert. Butyl, methoxy, ethoxy, trifluoromethyl and / or trifluoromethoxy,
  • R 4 and R 5 independently of one another are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, 2-chloroethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, Allyl, propargyl,
  • each of the cycloalkyl radicals may be substituted once or twice, in the same way or differently, by fluorine, chlorine, bromine, methyl and / or ethyl,
  • phenyl which can be substituted once or twice, in the same way or differently, by fluorine, chlorine, bromine, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, trifluoromethyl and / or trifluoromethoxy,
  • phenylalkyl having 1 or 2 carbon atoms in the alkyl part, where the phenyl part can be substituted once or twice, in the same way or differently, by fluorine, chlorine, bromine, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, trifluoromethyl and / or Trifluoromethoxy,
  • R 5 together represent double-linked alkanediyl having 4 or 5 carbon atoms or together represent a radical of the formula - (CH 2 ) 2 -Y- (CH 2 ) 2 -, in which
  • Y represents oxygen, sulfur or NR 6 , where R 6 represents hydrogen, methyl, ethyl or benzyl.
  • thiophene-2-carboxylic acid derivatives which can be used according to the invention are known in some cases (cf. Structure List from Maybridge Chemical Company 1996).
  • R 1 represents halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, phenyl or phenoxy,
  • p stands for integers from 1 to 5 and
  • R 2 for a radical of the formula
  • X represents oxygen or sulfur
  • R 3 represents hydrogen, alkyl, alkenyl, haloalkyl, alkoxyalkyl, pyran-4-yl, thiopyran-4-yl, optionally substituted cycloalkyl, optionally substituted cycloalkylalkyl, optionally substituted phenyl or optionally substituted phenylalkyl
  • R 4 and R 5 independently of one another represent hydrogen, alkyl, haloalkyl, alkoxyalkyl, alkenyl, alkynyl, alkoxycarbonylalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted cycloalkylalkyl, optionally substituted phenyl, optionally substituted phenylalkyl or optionally substituted heterocyclyl or
  • R 4 and R 5 together represent double-linked alkanediyl having 4 to 6 carbon atoms or together represent a radical of the formula - (CH 2 ) 2 -Y- (CH 2 ) 2 -, in which
  • Y represents oxygen, sulfur or NR 6 ,
  • R 6 represents hydrogen or alkyl having 1 to 6 carbon atoms or benzyl.
  • Thiophene-2-carboxylic acid derivatives of the formula (I-a) can be prepared by
  • R 1 and p have the meanings given above,
  • R 3 and X have the meanings given above,
  • R 4 and R 5 have the meanings given above,
  • R 1 and R 2 are preferably or particularly preferably those radicals which have already been mentioned as preferred or particularly preferred in connection with the description of the thiophene-2-carboxylic acid derivatives of the formula (I)
  • thiophene-2-carboxylic acid chloride derivatives of the formula (II) required as starting materials when carrying out process (a) according to the invention are hitherto unknown. They can be prepared by using ethyl thiophene-2-carboxylic acid of the formula
  • R 1 and p have the meanings given above, with aqueous alkali metal hydroxide solutions, such as sodium hydroxide solution, in the presence of a diluent, such as ethanol, at temperatures between 10 ° C and 80 ° C, then acidified and the resulting acids of the formula
  • R 1 and p have the meanings given above,
  • chlorinating agents e.g. Thionyl chloride or oxalyl chloride
  • a diluent e.g. Methylene chloride
  • the thiophene-2-carboxylic acid ethyl ester of the formula (I-b) required as starting materials in the above process can be prepared by:
  • R 1 and p have the meanings given above,
  • R 1 and p have the meanings given above,
  • phosphorus oxychloride in the presence of a diluent, e.g. Dimethylformamide, at temperatures between -10 ° C and 100 ° C and
  • R 1 and p have the meanings given above,
  • Diluents e.g. Tetrahydrofuruan, at temperatures between 0 ° C and 60 ° C.
  • Suitable acid binders for carrying out the process (a, variant ⁇ ) according to the invention are all customary inorganic or organic bases.
  • Alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethylate, are preferably usable.
  • Potassium tert-butoxide sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate, calcium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, also ammonium hydroxide, ammonium acetate or ammonium carbonate and tertiary amines, such as trimethylamine, triethylamine, N, N-dimethylaniline, pyridine, N-methylpyridine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecane (DBU).
  • DABCO diazabicyclooctane
  • DBN diazabicyclonones
  • DBU diazabicycloundecane
  • Suitable diluents for carrying out the process (a, variant ⁇ ) are all customary inert organic solvents.
  • Aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, can preferably be used;
  • Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Nitriles such as acetonitrile, propionitrile or benzonitrile;
  • Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or he
  • the method (a, variant ⁇ ) according to the invention is also optionally in
  • Copper (I) salts such as copper (I) chloride are particularly suitable as such.
  • a suitable phase transfer catalyst such as, for example, 15-crown-5, 18-crown-6 or tris- [2- (2-methoxyethoxy) ethyl] amine, can be advantageous here.
  • reaction temperatures can be varied within a substantial range when carrying out the process (a, variant ⁇ ). In general, temperatures between -20 ° C and + 180 ° C, preferably at temperatures between 0 ° C and + 150 ° C.
  • the process (a) according to the invention is generally carried out under atmospheric pressure.
  • Alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert.
  • DABCO diazabicyclooctane
  • DBN diazabicyclonones
  • DBU diazabicyclonecene
  • Inert organic solvents are suitable as diluents for carrying out the process according to the invention (a, variant ⁇ ).
  • Aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, can preferably be used; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones, such as acetone, butanone or methyl isobutyl ketone; Nitriles, such as acetonitrile,
  • Propionitrile or benzonitrile Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; Esters such as methyl acetate or ethyl acetate or sulfoxides such as dimethyl sulfoxide.
  • the process (a, variant ⁇ ) according to the invention can optionally also be carried out in a two-phase system, such as water / toluene or water / dichloromethane, if appropriate in the presence of a suitable phase transfer catalyst.
  • suitable phase transfer catalysts are: tetra-butylammonium iodide, tetrabutylammonium bromide, tetrabutylammonium chloride, tributyl-methylphosphonium bromide, trimethyl-C 13 / C 15 -alkylammonium chloride,
  • reaction temperatures can be varied within a substantial range when carrying out the process (a, variant ⁇ ). In general, temperatures between -20 ° C and 150 ° C, preferably at temperatures between 0 ° C and 120 ° C.
  • Fungicides can be used in crop protection to control Plasmodiophoromyces, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidomycetes and Deuteromycetes.
  • Bactericides can be used in crop protection to combat Psdeudomona daceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycaceae.
  • Xanthomonas species such as, for example, Xanthomonas campestris pv. Oryzae;
  • Pseudomonas species such as, for example, Pseudomonas syringae pv. Lachrymans; Erwinia species such as) Erwinia amylovora;
  • Pythium species such as, for example, Pythium ultimum
  • Phytophthora species such as, for example, Phytophthora infestans
  • Pseudoperonospora species such as, for example, Pseudoperonospora humuli or
  • Plasmopara species such as, for example, Plasmopara viticola
  • Bremia species such as, for example, Bremia lactucae
  • Peronospora species such as, for example, Peronospora pisi or P. brassicae;
  • Erysiphe species such as, for example, Erysiphe graminis
  • Sphaerotheca species such as, for example, Sphaerotheca fuliginea
  • Podosphaera species such as, for example, Podosphaera leucotricha
  • Venturia species such as, for example, Venturia inaequalis
  • Pyrenophora species such as, for example, Pyrenophora teres or P. graminea
  • Drechslera (Conidial form: Drechslera, Syn: Helminthosporium);
  • Cochliobolus species such as, for example, Cochliobolus sativus (conidial form: Drechslera, Syn: Helminthosporium);
  • Uromyces species such as, for example, Uromyces appendiculatus
  • Puccinia species such as, for example, Puccinia recondita
  • Sclerotinia species such as, for example, Sclerotinia sclerotiorum
  • Tilletia species such as, for example, Tilletia caries
  • Ustilago species such as, for example, Ustilago nuda or Ustilago avenae; Pellicularia species, such as, for example, Pellicularia sasakii; Pyricularia species, such as, for example, Pyricularia oryzae; Fusarium species, such as, for example, Fusarium culmorum;
  • Botrytis species such as, for example, Botrytis cinerea; Septoria species, such as, for example, Septoria nodorum; Leptosphaeria species, such as, for example, Leptosphaeria nodorum; Cercospora species, such as, for example, Cercospora canescens; Alternaria species, such as, for example, Alternaria brassicae;
  • Pseudocercosporella species such as, for example, Pseudocercosporella herpotricoids.
  • the active ingredients which can be used according to the invention can be used with particularly good results in combating diseases in wine, fruit and vegetable cultivation, such as, for example, against Phytophthora species. Cereal diseases, such as Erysiphe species, or rice diseases, such as Pyricularia species, are also successfully combated. Furthermore, the compounds which can be used according to the invention can also be used to increase the crop yield of crop plants.
  • the substances which can be used according to the invention can be used to protect technical materials against attack and destruction by undesired microorganisms.
  • technical materials are to be understood as non-living materials that have been prepared for use in technology.
  • technical materials which are to be protected against microbial change or destruction by active substances according to the invention can be adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which are attacked or decomposed by microorganisms can be.
  • Parts of production plants, for example, are also part of the materials to be protected Cooling water circuits, called, which can be impaired by the multiplication of microorganisms.
  • technical materials are preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer liquids.
  • Bacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can cause degradation or a change in the technical materials.
  • the active substances or agents according to the invention preferably act against fungi, in particular mold, and against slime organisms and algae.
  • microorganisms of the following genera may be mentioned:
  • Alternaria such as Alternaria tenuis
  • Aspergillus such as Aspergillus niger
  • Chaetomium such as Chaetomium globosum
  • Coniophora such as Coniophora puetana
  • Lentinus such as Lentinus tigrinus
  • Penicillium such as Penicillium glaucum
  • Polyporus such as Polyporus versicolor
  • Aureobasidium such as Aureobasidium pullulans
  • Sclerophoma such as Sclerophoma pityophila
  • Trichoderma like Trichoderma viride
  • Escherichia such as Escherichia coli
  • Pseudomonas such as Pseudomonas aeruginosa
  • Staphylococcus such as Staphylococcus aureus.
  • the active compounds can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV Cold and warm fog formulations.
  • extenders that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or Dispersing agents and / or foaming agents.
  • surface-active agents that is to say emulsifiers and / or Dispersing agents and / or foaming agents.
  • organic solvents can, for example, also be used as auxiliary solvents.
  • liquid solvents aromatics such as xylene, toluene, alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as Butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide or dimethyl sulfoxide and water.
  • aromatics such as xylene, toluene, alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylene or methylene chloride
  • aliphatic hydrocarbons such as cyclohexane or paraffins
  • Carriers are meant liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide.
  • Solid carrier materials are suitable: for example natural rock powder, such as kaolins, clay earths, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates.
  • Possible solid carriers for granules are: e.g.
  • Suitable emulsifiers and / or foaming agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates.
  • Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes, such as alizarin, azo and metal phthalocyanine dyes and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc, can be used.
  • the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds which can be used according to the invention, as such or in their formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the spectrum of activity or to prevent the development of resistance.
  • synergistic effects are obtained, i.e. the effectiveness of the mixture is greater than the effectiveness of the individual components.
  • Diethofencarb Difenoconazol, Dimethirimol, Dimethomorph, Diniconazol, Diniconazol-M, Dinocap, Diphenylamine, Dipyrithione, Ditalimfos, Dithianon, Dodemorph, Dodine, Drazoxolon, Ediphenphos, Epoxiconazol, Etaconazam, Fenirazolol, Ethiriazolol, Ethiriazolol, Ethiradololox, Fenitropan,
  • Mancopper Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl,
  • Metconazole methasulfocarb, methfuroxam, metiram, metomeclam, metsulfovax,
  • Oxadixyl Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,
  • Paclobutrazole pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin
  • Tebuconazole Tebuconazole, tecloftalam, technazen, tetcyclacis, tetraconazole, thiabendazole,
  • Insecticides / acaricides / nematicides Abamectin, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz,
  • Fenamiphos Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate,
  • Fipronil Fluazinam, Fluazuron, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufen- prox, Fluvalinate, Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb,
  • Parathion A Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet,
  • Promecarb Propaphos, Propoxur, Prothiophos, Prothoat, Pymetrozin, Pyrachlophos, Pyridaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen,
  • Tebufenozide Tebufenpyrad
  • Tebupirimphos Teflubenzuron
  • Tefluthrin Temephos
  • Terbam Terbufos
  • Tetrachlorvinphos Thiafenox, Thiodicarb
  • Triazophos triazuron, trichlorfon, triflumuron, trimethacarb,
  • the active compounds can be used as such, in the form of their commercially available formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the customary manner, for example by watering, spraying, atomizing, scattering, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume process or to add the active ingredient preparation or the active ingredient itself to the soil inject. The seeds of the plants can also be treated.
  • the active compound concentrations in the use forms can be varied within a substantial range: they are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.
  • amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.
  • active ingredient concentrations are from 0.00001 to
  • 0.1% by weight preferably from 0.0001 to 0.02% by weight, is required at the site of action.
  • the agents used to protect industrial materials generally contain the active ingredients in an amount of 1 to 95%, preferably 10 to 75%.
  • the application concentrations of the active compounds which can be used according to the invention depend on the type and the occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimal amount can be determined by test series. In general, the application concentrations are in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based on the material to be protected.
  • a mixture of 213 g (1.5 mol) of trifluoroacetic acid ethyl ester and 175 g (1.5 mol) of benzyl cyanide is added dropwise at room temperature with stirring in 510 g (1.5 mol) of a 20% solution of sodium ethylate in ethanol.
  • the mixture is heated under reflux for 16 hours, allowed to cool, the reaction mixture is poured onto ice water and 150 ml of hydrochloric acid are added.
  • the resulting mixture is extracted several times with methyl tert-butyl ether.
  • the combined organic phases are dried over sodium sulfate and then concentrated under reduced pressure. In this way, ⁇ -trifluoroacetyl-phenyl-acetonitrile is obtained.
  • the plants are placed in a greenhouse at a temperature of approx. 20 ° C and a relative air humidity of approx. 80% in order to promote the development of mildew pustules
  • Emulsifier 0.6 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • the plants are then sprayed with the preparation of active compound in the stated application rate.
  • the plants are placed in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80%.

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

Abstract

L'invention concerne de nouveaux microbicides à base de dérivés, partiellement connus, d'acide thiophène-2-carboxylique de la formule (I), dans laquelle R1, R2 et n ont la signification donnée dans la description, ainsi que l'utilisation de ces dérivés pour lutter contre des micro-organismes non désirés. L'invention concerne également de nouveaux dérivés d'acide thiophène-2-carboxylique de la formule (I-a), dans laquelle R1, R2 et p ont la signification donnée dans la description, ainsi que des procédés de production des dérivés de la formule (I-a).
PCT/EP1997/006368 1996-11-27 1997-11-14 Microbicides a base de derives d'acide thiophene-2-carboxylique WO1998023605A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP97951205A EP0944615A1 (fr) 1996-11-27 1997-11-14 Microbicides a base de derives d'acide thiophene-2-carboxylique
JP52422098A JP2001504832A (ja) 1996-11-27 1997-11-14 チオフェン―２―カルボン酸誘導体に基づく殺微生物剤
US09/308,903 US6013664A (en) 1996-11-27 1997-11-14 Microbicidal agents based on thiophene-2-carboxylic acid derivatives
AU54824/98A AU5482498A (en) 1996-11-27 1997-11-14 Microbicidal agents based on thiophene-2-carboxylic acid derivatives

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1996149093 DE19649093A1 (de) 1996-11-27 1996-11-27 Mikrobizide Mittel auf Basis von Thiophen-2-carbonsäure-Derivaten
DE19649093.6 1996-11-27

Publications (1)

Publication Number Publication Date
WO1998023605A1 true WO1998023605A1 (fr) 1998-06-04

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JP (1) JP2001504832A (fr)
AU (1) AU5482498A (fr)
DE (1) DE19649093A1 (fr)
WO (1) WO1998023605A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003007923A2 (fr) * 2001-07-18 2003-01-30 Solvay Pharmaceuticals Gmbh Utilisation de derives de phenyle, de phenol et de benzoyle substitues par trifluoroacetylalkyle dans le traitement et la prophylaxie de l'obesite de ses maladies associees et/ou secondaires accompagnant l'obesite
EP1493739A1 (fr) * 2003-07-03 2005-01-05 Warner-Lambert Company LLC Dérivés thiophényliques d'aminoacides, leur procédé de préparation et les compositions pharmaceutiques qui les contiennent
WO2005066138A1 (fr) * 2003-12-22 2005-07-21 Bayer Cropscience Ag Amides heterocycliques substitues a effet fongicide
CN113166093A (zh) * 2018-10-08 2021-07-23 韩国化学研究院 噻吩甲酰胺衍生物和包含其的植物病害控制剂

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112012023759B1 (pt) 2010-03-23 2018-10-09 Basf Se compostos de piridazina, método para controlar pragas invertebradas, método para proteger material de propagação de planta e material de propagação de planta

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Publication number Priority date Publication date Assignee Title
EP0450355A1 (fr) * 1990-04-06 1991-10-09 Degussa Aktiengesellschaft Composés pour la lutte contre des maladies des plantes
EP0538231A1 (fr) * 1991-10-18 1993-04-21 Monsanto Company Fongicides pour contrôle des maladies des racines des plantes
WO1995027397A1 (fr) * 1994-04-11 1995-10-19 Bayer Aktiengesellschaft Microbicides a base de derives d'acide dibromothiophenecarboxylique
US5484807A (en) * 1991-12-04 1996-01-16 American Cyanamid Co Haloalkylthio, -sulfinyl and -sulfonyl arylpyrrole insecticidal and acaricidal agents

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
EP0450355A1 (fr) * 1990-04-06 1991-10-09 Degussa Aktiengesellschaft Composés pour la lutte contre des maladies des plantes
EP0538231A1 (fr) * 1991-10-18 1993-04-21 Monsanto Company Fongicides pour contrôle des maladies des racines des plantes
US5484807A (en) * 1991-12-04 1996-01-16 American Cyanamid Co Haloalkylthio, -sulfinyl and -sulfonyl arylpyrrole insecticidal and acaricidal agents
WO1995027397A1 (fr) * 1994-04-11 1995-10-19 Bayer Aktiengesellschaft Microbicides a base de derives d'acide dibromothiophenecarboxylique

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Title
R. ARNAUD ET. AL.: "Reactivity of trifluoromethyl enones in Michael Additions.", BULLÉTIN DE LA SOCIÉTÉ CHIMIQUE DE FRANCE, vol. 131, no. 8, August 1994 (1994-08-01), PARIS, FR, pages 844 - 53, XP002057686 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003007923A2 (fr) * 2001-07-18 2003-01-30 Solvay Pharmaceuticals Gmbh Utilisation de derives de phenyle, de phenol et de benzoyle substitues par trifluoroacetylalkyle dans le traitement et la prophylaxie de l'obesite de ses maladies associees et/ou secondaires accompagnant l'obesite
WO2003007923A3 (fr) * 2001-07-18 2004-01-08 Solvay Pharm Gmbh Utilisation de derives de phenyle, de phenol et de benzoyle substitues par trifluoroacetylalkyle dans le traitement et la prophylaxie de l'obesite de ses maladies associees et/ou secondaires accompagnant l'obesite
US6930207B2 (en) * 2001-07-18 2005-08-16 Solvay Pharmaceutical Gmbh Trifluoroacetylalkyl-substituted phenyl, phenol and benzoyl compounds and related methods of treatment
EP1493739A1 (fr) * 2003-07-03 2005-01-05 Warner-Lambert Company LLC Dérivés thiophényliques d'aminoacides, leur procédé de préparation et les compositions pharmaceutiques qui les contiennent
WO2005003115A1 (fr) * 2003-07-03 2005-01-13 Warner-Lambert Company Llc Derives d'acide amine thiophenique, leur procede de preparation et compositions pharmaceutiques les contenant
WO2005066138A1 (fr) * 2003-12-22 2005-07-21 Bayer Cropscience Ag Amides heterocycliques substitues a effet fongicide
CN113166093A (zh) * 2018-10-08 2021-07-23 韩国化学研究院 噻吩甲酰胺衍生物和包含其的植物病害控制剂

Also Published As

Publication number Publication date
EP0944615A1 (fr) 1999-09-29
DE19649093A1 (de) 1998-05-28
JP2001504832A (ja) 2001-04-10
AU5482498A (en) 1998-06-22

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