EP2378880A1 - Utilisation de 5-pyridine-4-yl(1,3)thiazoles pour la lutte contre les champignons phytopathogènes - Google Patents

Utilisation de 5-pyridine-4-yl(1,3)thiazoles pour la lutte contre les champignons phytopathogènes

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Publication number
EP2378880A1
EP2378880A1 EP09764746A EP09764746A EP2378880A1 EP 2378880 A1 EP2378880 A1 EP 2378880A1 EP 09764746 A EP09764746 A EP 09764746A EP 09764746 A EP09764746 A EP 09764746A EP 2378880 A1 EP2378880 A1 EP 2378880A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
amino
phenyl
haloalkyl
alkoxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09764746A
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German (de)
English (en)
Inventor
Amos Mattes
Ruth Meissner
Klaus Tietjen
Christoph Andreas Braun
Peter Dahmen
Martin Kaussmann
Peter Schreier
Arnd Voerste
Ulrike Wachendorff-Neumann
Hans-Georg Schwarz
Jürgen BENTING
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer Intellectual Property GmbH
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Bayer CropScience AG
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Publication date
Application filed by Bayer CropScience AG filed Critical Bayer CropScience AG
Priority to EP09764746A priority Critical patent/EP2378880A1/fr
Publication of EP2378880A1 publication Critical patent/EP2378880A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to the use of known 5-pyridin-4yl (l, 3) thiazoles for controlling phytopathogenic fungi and for the reduction of mycotoxins in plants and parts of plants, as well as methods for controlling phytopathogenic fungi and for the reduction of mycotoxins in plants and plant parts in crop protection, as well as pesticides containing these 5-Pyridin ⁇ yl (l, 3) thiazoles.
  • 5-pyridin-4yl (1,3) thiazoles as such are already known as pharmaceutically active compounds (see, for example: WO99 / 21555, WO99 / 64418, JP05070446, WO01 / 30778, WO01 / 74811,
  • R 1 is hydrogen, an optionally substituted by hydroxy, amino, cyano, C r C 4 alkoxy, R 5 , OR 5 , (C r C 4 alkyl) sulfanyl, (Ci-C 4 alkyl) sulfinyl, (C , -C 4 alkyl) sulfonyl, (Ci-C 4 alkyl) amino, bis (Ci-C 4 alkyl) amino, Ci-C 4 alkylcarbonyloxy, Ci-Q-alkylcarbonylamino, NHCOR 5 or OCOR 5 substituted Ci C 8 alkyl,
  • N CR 6 N (R 6 ) 2 , NR 6 COR 6 , NR 6 CO (CH 2 ) ra OR 6 , NR 6 COCH (C r C 4 alkyl) OR 6 , NR 6 CO (CH 2 ) m N (R 6 ) 2 , NR 6 CO (CH 2 ) m COOR 6 , NR 6 COOR 7 , NR 6 CON (R 6 ) 2 , NR 6 CO (CH 2 ) ,, ⁇ , NR 6 CCHz) 1n R 8 , NR 6 SO 2 R 6
  • R 1 is a saturated or partially saturated, five- to seven-membered, unsubstituted or optionally mono- or polysubstituted by oxo, hydroxy, halogen, Ci-C 6 alkyl, Q -C 4 - haloalkyl, C r C 4 alkoxy, C r C 6 alkylcarbonyl QQ-haloalkylcarbonyl, C r C 6 alkoxycarbonyl or with a phenyl optionally substituted by halogen or Ci-C 4 alkyl-substituted heterocycle, which may contain up to four heteroatoms selected from N, O and S, wherein two Oxygen atoms are not adjacent
  • R 1 is a five-membered heteroaromatic which may contain up to three heteroatoms selected from N, O and S, where two oxygen atoms or two nitrogen atoms are not are nachbart and optionally mono- or polysubstituted by identical or different radicals from the group halogen, hydroxy, cyano, C C4alkyl, Ci-C 4 haloalkyl, C r C 4 - alkoxy, Ci-C4-haloalkoxy, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 -alkylcarbonyl or phenyl
  • R 1 is a six-membered heteroaromatic radical which may contain up to four heteroatoms selected from N, O and S, where two oxygen atoms are not adjacent and which may be mono- or polysubstituted by halogen, hydroxy, cyano, C 1 -C 4 -alkyl, C] -C 4 - haloalkyl, CpC 4 -alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylcarbonyl, Ci-C 4 -alkoxycarbonyl or phenyl;
  • R 2 is a five- or six-membered heteroaromatic compound which may contain up to four heteroatoms selected from N, O and S, where two oxygen atoms are not adjacent and which may be mono- or polysubstituted by identical or different radicals from the group
  • R 3 is hydrogen, halogen, cyano, hydroxy, OR 6, cyano, amino, Ci-C 6 alkyl, C r C 8 - haloalkyl, (CH 2) m OR 6, (CH 2) m CN, (CH ⁇ CR 6 ); COOR 6 , CON (R 6 ) 2 , SR 6 , SOR 6 , S (O) 2 R 6 ,
  • R 4 is hydrogen or C 1 -C 4 -alkyl or, together with R 3 , forms a five- or six-membered mono- or polyunsaturated cycle which may contain a nitrogen atom via the pyridine radical to which they are bonded; - A -
  • R 5 represents a phenyl radical which is optionally substituted with halogen, hydroxy, cyano, Ci-Q-alkyl, Ci-C 4 alkoxy, -C 2 -haloalkoxy, Ci-C 2 haloalkyl, Ci-C 4 alkoxycarbonyl, carboxy, is substituted;
  • R 6 is independently hydrogen, CpC ⁇ -alkyl, optionally substituted with Ci-C 4 alkyl or halo C 3 -C 6 cycloalkyl, C r C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 -
  • two radicals R 6 are a 3 to 7-membered, unsubstituted or optionally mono- or polysubstituted by identical or different radicals from the group halogen, cyano, CpC 4 -alkyl, CpC 4 haloalkyl, CpC 4 -
  • Alkoxy, CpC 4 -haloalkoxy, CpC 4 -alkylcarbonyl or CpC 4 -alkoxycarbonyl-substituted, saturated or unsaturated cycle which may contain up to four further heteroatoms selected from N, O and S wherein two oxygen atoms are not adjacent
  • R 6 is a 3 to 7-membered, unsubstituted or optionally mono- or polysubstituted by identical or different radicals from the group of halogen, hydroxy, CpC 4 -alkyl, Cp C 4 -haloalkyl, C r C 4 -alkoxy, CpC 4 - Haloalkoxy or phenyl substituted, saturated or unsaturated cycle, which may contain up to four other heteroatoms selected from N, O and S, wherein two oxygen atoms are not adjacent or
  • two R 6 s in the case where two R 6 s are attached to one sulfur atom, two R 6 s form a 5 to 7 membered, unsubstituted or optionally C r C 4 alkyl substituted cycle containing up to two further heteroatoms selected from N , O and S, where two oxygen atoms are not adjacent;
  • R 7 independently of one another Ci-C ⁇ -alkyl, optionally substituted with Ci-C 4 alkyl or halo C 3 -C 6 cycloalkyl, C r C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 -alkynyl, C r C 4 - alkoxy (C r C4) alkyl, hydroxy (C r C4) alkyl,
  • Ci-C4-alkylcarbonyl carboxy, or C r C 4 alkoxycarbonyl substituted aryl or aryl (Ci-C 4) alkyl,
  • Alkoxycarbonyl substituted, saturated or unsaturated cycle which may contain no or up to four heteroatoms selected from N, O and S, where two oxygen atoms are not adjacent,
  • R 8 represents a 3- to 7-membered, saturated, unsaturated or aromatic mono- or bi-cycle which may contain no or up to four heteroatoms selected from N, O and S, where two oxygen atoms are not adjacent and the optionally with oxo,
  • Phenyl carboxy, CpC ⁇ alkylcarbonyl or C r C 6 alkoxycarbonyl
  • R 9 represents a 3- to 7-membered, unsubstituted or optionally mono- or polysubstituted by identical or different radicals from the group consisting of C 1 -C 4 -alkyl, halogen, cyano, CpC 4 -
  • n 1 and 6
  • Inventive 5-pyridin-4yl (l, 3) thiazoles of the formula (I) and, if appropriate, their salts are very well suited for controlling phytopathogenic harmful fungi and for reducing mycotoxins in plants and plant parts.
  • the abovementioned compounds according to the invention exhibit fungicidal and mycotoxin-reducing activity and can be used both in crop protection, in the household and hygiene sector and in the protection of materials.
  • the 5-pyridin-4yl (1,3-thiazoles) which can be used according to the invention are generally defined by the formula (I).
  • Preferably used are 5-pyridin-4yl (l, 3) thiazoles of the formula (I) in which the radicals have the following meanings.
  • R 1 is preferably hydrogen, C 1 -C 6 -alkyl, C r C 4 haloalkyl, C 3 -C 8 cycloalkyl, aryl (C r C4) alkyl, formyl, (Ci-C 4 alkyl) carbonyl, (C r C 4 haloalkyl) carbonyl, COOH, (C r C 4 alkoxy) carbonyl, (C 3 -C 6 alkenyl-oxy) carbonyl, (C 3 -C 6 alkynyl-oxy) carbonyl, (C -C 4- alkyl) carbamoyl, bis (C r C 4 alkyl) carbamoyl, (CrO-AlkenyOcarbamoyl, (C 3 -C 4 AIkUIyI) CaTbBmOyI, CONHR 10, C 1 - C 6 hydroxyalkyl, C 1 -C 4 alkoxy (C r C4) alkyl, phen
  • C 4 alkyl) COR 10 N (C 3 -C 5 -alkynyl) CO (R 10), NHCONH (C 1 - C 4 AIlCyI), NHCON (C 1 -C 4 AIlCyI) 2, NHCONHR 10, NHCO (R 11), N (C 1 -C 4 -alkyl) CO (R 11 ); or
  • R 1 is preferably a saturated or partially saturated heterocycle selected from the group: pyrrolidine, imidazolidine, oxazolidine, piperidine, piperazine, Mo ⁇ holin, diazepan, each unsubstituted or optionally with oxo, halogen, Ci-C 4 alkyl, Ci-C 4 Alkoxy, phenyl, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 -alkoxycarbonyl or hydroxy;
  • R 1 is preferably a phenyl radical which is optionally mono- or polysubstituted by identical or different radicals from the group halogen, cyano, hydroxy, C r C 4 alkyl, Ci-C 4 alkoxy, Ci-C4-haloalkoxy, C r C 4 haloalkyl, C r C 4 alkylsulfonyl, C r C 4 alkylsulfinyl, C 1 -C 4 - alkylsulfanyl, C r C 4 alkylcarbonyl, Ci-C 4 alkoxycarbonyl, carboxy, carbamoyl, C r C 4 -
  • Alkylcarbamoyl bis (Ci-C 4 alkyl) carbamoyl or (C 3 -C 4) alkenylcarbamoyl groups;
  • R 1 is preferably a heteroaromatic radical selected from the group: furan, thiophene, thiazole, pyridine din, which in each case unsubstituted or optionally substituted with fluorine, chlorine, cyano, Ci-C 4 -alkyl, Q-C 4 alkoxy, C i - C 4 alkycarbonyl, C 1 -C 4 alkoxycarbonyl or hydroxy;
  • R 2 is preferably a phenyl or naphthalenyl radical which is optionally mono- or polysubstituted by identical or different radicals from the group consisting of halogen, cyano, hydroxyl, C 1 -C 0 -alkyl, C 3 -C 6 -cycloalkyl, C 1 - C 4 alkoxy, (C r C4) alkoxy (Ci-C 4) alkyl, benzyloxy, CpC 4 - haloalkyl, C r C 4 haloalkoxy, Methandiylbisoxy, Difluormethandiylbisoxy, propane-l, 3-diyl, NH (Ci- is substituted C 4 alkyl), N (C 1 -C 4 -alkyl) 2, (C r C4) alkylsulfanyl, (C, -C 4) alkoxycarbonyl, carboxyl,
  • heteroaromatic selected from the group: furan, thiophene, pyridine, which in each case unsubstituted or optionally substituted with fluorine, chlorine, Ci-C 4 alkyl or C r C 4 alkoxy;
  • R 3 is preferably hydrogen, fluorine, chlorine, hydroxyl, amino, cyano, (C r C4) alkyl, (C, -C 4) - haloalkyl, (C r C 4) alkoxy, hydroxymethyl, cyanomethyl, 1-pyrrolidine ylmethyl, fanyl Phenylsul-, benzylsulfanyl, phenylsulfonyl, (Ci-C 4) alkoxycarbonyl, (Ci-GOAlkylcarbamoyl, bis (Ci-C 4) alkylcarbamoyl, NH (Cj-C4 alkyl), N (Ci-C 4 alkyl ) 2 , NH (C r C 4 haloalkyl), (C 1 -C 2 ) alkoxy (C 1 -C 4 ) alkylamino, hydroxy (C 1 -C 4 ) alkylamino, NH (C 3 -C 5
  • R 3 is preferably a heterocycle selected from the group: pyrrolidine, piperidine, piperazine, morpholine, which is in each case unsubstituted or optionally substituted by oxo, halogen, (Cj-C 4 ) alkyl;
  • R 4 is preferably hydrogen, methyl or together with R 3 and the pyridine ring to which both are bonded form a bicyclic selected from the group quinolin-4-yl, 1,8-naphthyridin-4-yl, 1H-pyrrolo 2,3-b] pyridin-4-yl,
  • R 10 preferably represents a phenyl radical which is optionally substituted by halogen, hydroxy, cyano, Ci- C 4 alkyl, C r C 4 alkoxy, C r C 2 -haloalkoxy, C r C 2 haloalkyl, C r C 4 -alkoxycarbonyl Carboxy is substituted;
  • R 11 preferably represents a heteroaromatic selected from the group of furan, thiophene, Py ridin, pyrazine, optionally substituted by fluorine, chlorine, cyano, C r C 4 alkyl, C 1 -C 4 -alkoxy, C 1 - C 2- haloalkyl, Ci-C 4 alkoxycarbonyl is substituted;
  • R 12 preferably represents a phenyl or Naphthalinylrest, optionally substituted with halo, (C r C4) alkyl (C r C 4) alkoxy, (C r C4) -haloalkyl groups;
  • R 1 is 2 haloalkyl particularly preferably hydrogen, CPCE-alkyl, Ci-C, C 3 -C 6 cycloalkyl, A- ryl (C r C4) alkyl, formyl, (C 1 -C 4 alkyl) carbonyl, (C 1 -C 2 -haloalkyl) carbonyl, COOH, (C r C 4 -
  • R 1 is particularly preferably a saturated or partially saturated heterocycle selected from the group consisting of pyrrolidine, imidazolidine, oxazolidine, piperidine, piperazine, morpholine, diazepan, each of which is unsubstituted or optionally substituted by oxo, fluoro, chloro, C 1 -C 4 -alkyl, C 4 alkoxy, phenyl, C r C 4 alkycarbonyl, C r C 4 alkoxycarbonyl or hydroxy;
  • R 1 is particularly preferably a phenyl radical which is optionally mono- or polysubstituted by identical or different radicals from the group fluorine, chlorine, bromine, hydroxy, Ci-C 4 alkyl, C 1 -C 4 -
  • R 1 is particularly preferably a heteroaromatic radical selected from the group: furan, thiophene, Py ridin, which in each case unsubstituted or optionally substituted with fluorine, chlorine, C r C 4 alkyl, C r C 4 - alkoxy, Ci-C 4 -Alkycarbonyl , CrQ-alkoxycarbonyl or hydroxy is substituted;
  • R 2 is particularly preferably a phenyl or naphthalenyl radical which is optionally mono- or polysubstituted by identical or different radicals from the group consisting of halogen, cyano, hydroxyl,
  • Haloalkoxy methanediylbisoxy, difluoromethanediylbisoxy, propan-l, 3-diyl, NH (C 1 -C 4 -alkyl),
  • R 2 is particularly preferably a heteroaromatic selected from the group furan, thiophene, pyridine, which is in each case unsubstituted or optionally substituted by fluorine, chlorine, C 1 -C 4 -alkyl, substituted;
  • R 3 is particularly preferably hydrogen, fluorine, chlorine, hydroxyl, amino, cyano, (Ci-C 2) alkyl, (Ci-C 2) -haloalkyl, (Ci-C 2) alkoxy, hydroxymethyl, cyanomethyl, 1-pyrrolidine ylmethyl, phenylsulfanyl, benzylsulfanyl, phenylsulfonyl, (C r C4) alkoxycarbonyl, NH (C r C 4 alkyl),
  • R 3 is particularly preferably a heterocycle selected from the group: pyrrolidine, piperidine, piperazine, morpholine, which is in each case unsubstituted or optionally substituted by methyl;
  • R 4 is particularly preferably hydrogen, methyl or together with R 3 and the pyridine ring to which they are bonded form a bicyclic selected from the group quinolin-4-yl, 1,8-naphthyridin-4-yl, 1H -pyrrolo [2,3-b] pyridin-4-yl
  • R 10 particularly preferably represents a phenyl radical which is optionally substituted by fluorine, chlorine, hydro- xy, cyano, C r C 4 alkyl, C r C 4 alkoxy, C r C 2 -haloalkoxy, C r C 2 -haloalkyl C 1 -C 4 alkoxycarbonyl, carboxy, is substituted;
  • R 11 particularly preferably represents a heteroaromatic radical selected from the group furan, thiophene, pyridine, pyrazine, which is optionally substituted by chlorine, methyl, methoxy;
  • R 12 particularly preferably represents a phenyl or naphthalenyl radical which is optionally substituted by fluorine, chlorine, methyl, methoxy, trifluoromethyl,
  • n stands for a number between 1 and 4;
  • R 1 very particularly preferably represents hydrogen
  • phenyl 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 3,5-dimethylphenyl, 2,4-dimethylphenyl, 3,4-dimethylphenyl, 4-ethylphenyl, 4- / propylphenyl, 4-f-butylphenyl, 4-methoxyphenyl , 2-methoxyphenyl, 3-methoxyphenyl, 3,4-dimethoxyphenyl, 3,5-dimethoxyphenyl, 3,4,5-trimethoxyphenyl, 4-ethoxyphenyl, A-
  • NHPh 4-fluoro-phenylamino, 2-fluoro-phenylamino, 3,5-dichloro-phenylamino, 2-methyl-phenylamino, 4-methyl-phenyl-naphtho, 3-cyanophenyl-amino, 3-trifluoromethyl-phenyl-amino,
  • phenyl is very particularly preferably phenyl, naphthalen-1-yl, naphthalen-2-yl, 2,3-dihydro-1H-inden-5yl 4-chlorophenyl, 3-chlorophenyl, 2-chlorophenyl, 4-fluorophenyl, 3-fluorophenyl, 2-Fluoro-phenyl, 4-bromophenyl, 3-bromophenyl, 3,5-dichloro-phenyl, 2,4-difluorophenyl, 2,6-difluorophenyl, 2,4,6-trifluorophenyl, 3,4-dichloro-phenyl, 2-chloro-4 fluo ⁇ henyl, 3-cyanophenyl, 4-cyanophenyl, 4-hydroxyphenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 3,5-dimethylphenyl, 3,4-dimethylphenyl, 4-ethylphenyl, 3-
  • R 3 very particularly preferably represents hydrogen, fluorine, chlorine, hydroxyl, methoxy, cyano, methyl, chloromethyl, hydroxymethyl, cyanomethyl, pyrrolidin-1-ylmethyl, COOMe, COOEt, phenylsulfanyl, benzylsulfanyl, phenylsulfonyl, amino, NHMe, NHEt , NHPr, NHBu,
  • NHCH 2 CH CH 2 , NHCH 2 CCH, cyclopropylamino, cyclobutylamino, cyclohexylamino, cyclopentylamino, cyclohexyl (methyl) amino, 4-methylpiperazin-1-yl, piperidin-1-yl, pyrrolinedin-1-yl, monochlorin-1-yl, NMe 2 , NEt 2 , NHCH 2 CH 2 OCH 3 , NHCH (Me) CH 2 OCH 3 , NHCOPh, (thiophen-2-ylcarbonyl) amino, (naphthalenylcarbonyl) amino, NHCOMe, NHCOEt, NHCOfBu, cyclopentylcarbonylamino, cyclohexylcarbonylamino, NHCO (CH 2 ) 2 CH 3 ,
  • R 4 very particularly preferably represents hydrogen, methyl or forms, together with R 3 and the pyridine ring to which both are bonded, a bicyclic selected from the group consisting of quinolin-4-yl, 1,8-naphthyridin-4-yl, 1H- pyrrolo [2,3-b] pyridin-4-yl,
  • R 1 particularly preferably represents hydrogen
  • NHCOMe, NHCOEt, NHCOPr, NHCOBu, NHCOfBu, NHCOCHMe 2 , NHCOCH 2 CHMe 2 , NHCOCH CH 2 , acetyl (methyl) amino, acetyl (ethyl) amino, acetyl (propyl) amino, acetyl (/ - propyl) amino, acetyl (butyl) amino, acetyl (phenyl) amino, acetyl (pentyl) amino, acetyl (benzyl) amino, cyclopentylcarbonylamino, cyclohexylcarbonylamino, cyclopentylacetylamino, phenylacetylamino, 3-phenylpropanoylamino, phenylcarbonylamino, methyl (phenylcarbonyl) amino, ethyl (phenylcarbonyl) amino, propyl (pheny
  • phenyl is particularly particularly preferably phenyl, naphthalen-1-yl, 4-chlorophenyl, 3-chlorophenyl, 2-chlorophenyl, 4-fluorophenyl, 3-fluorophenyl, 4-bromophenyl, 3-bromophenyl, 3,5-dichloro-phenyl, 3, 4-dichlorophenyl, 3-cyanophenyl, 4-hydroxyphenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 3,5-dimethylphenyl, 3,4-dimethylphenyl, 4-ethylphenyl, 3-ethylphenyl, 4-propylphenyl, 3 Propylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-t-butylphenyl, 4-hexylphenyl, 4-fluoro-3-methylphenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphen
  • R 3 particularly particularly preferably represents hydrogen, fluorine, chlorine, hydroxyl, methyl, chloromethyl, hydroxymethyl, cyanomethyl, pyrrolidin-1-ylmethyl, COOMe, phenylsulfanyl, benzylsulfanyl, phenylsulfonyl, amino, cyclohexylamino, cyclopentylamino, cyclohexyl ( methyl) amino, 4-methyl-piperazin-1-yl, piperidin-1-yl, pyrrolidin-1-yl, morpholin-1-yl, NHCOPh, (thiophen-2-ylcarbonyl) -amino, (naphthalen-1-ylcarbonyl) -amino, NHCOMe, NHCOEt, NHCOrBu, cyclopentylcarbonylamino, cyclohexylcarbonylamino, NHCOPr,
  • R 4 particularly particularly preferably represents hydrogen
  • R 2 is phenyl which is substituted by halogen or C 1 -C 4 -alkyl
  • R 2 is a thiophene or furan radical which is optionally mono- or polysubstituted by identical or different radicals from the group halogen, cyano, C 1 -C 2 -alkyl, C 1 -C 4 2- alkoxy, C 1 -C 2 -haloalkyl;
  • R 1 is Ci-C 6 alkyl, C r C 4 haloalkyl or C 3 -C 8 -Cyclalkyl
  • R 3 is N (R 2 , NR 6 COR 6 , NR 6 CO (CH 2 ) m R 9 .
  • Halogen fluorine, chlorine, bromine and iodine
  • Aryl unsubstituted or optionally substituted, 5 to 15-membered, partially or completely unsaturated mono-, bi- or tricyclic ring system having up to 3 ring members, wherein at least one of the rings of the ring system is completely unsaturated, such as (but not limited to ) Benzene, naphthalene, tetrahydronaphthalene, anthracene, indane,
  • Phenanthrene azulene
  • Alkyl saturated, straight-chain or branched hydrocarbon radicals having 1 to 10 carbon atoms, such as (but not limited to) methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl, 1,1-dimethylethyl, Pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-
  • Haloalkyl straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as mentioned above), where in these groups the hydrogen atoms may be partially or completely replaced by halogen atoms as mentioned above, for example (but not limited to) C 1 -C 2 - Haloalkyl such as chloromethyl, bromomethyl, dichloromethyl, trichloro methyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2 fluoroethyl, 2-chloro, 2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloro
  • Alkenyl unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 16 carbon atoms and at least one double bond in any position, such as (but not limited to) C 2 -C 6 alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1 Methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl,
  • Alkynyl straight-chain or branched hydrocarbon groups having 2 to 16 carbon atoms and at least one triple bond in any position, such as (but not limited to) C 2 -C 6 -alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2- Methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5- Hexynyl, 1-
  • Hydroxyalkyl straight-chain or branched alkyl groups (as mentioned above), in which groups a hydrogen atom may be replaced by a hydroxyl group, for example (but not limited to) C 1 -C 2 -hydroxyalkyl, such as hydroxymethyl, 1-hydroxyethyl or 2-hydroxyalkyl.
  • Alkoxy saturated, straight or branched alkoxy radicals having 1 to 4 carbon atoms, such as, but not limited to, C 1 -C 4 alkoxy, such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methyl-propoxy, 2-methylpropoxy 1,1-dimethylethoxy;
  • Alkoxyalkyl an alkoxy group (as mentioned above) attached to the skeleton via an alkyl group (as mentioned above) such as, but not limited to, methoxymethyl, methoxyethyl or ethoxyethyl;
  • Haloalkoxy straight-chain or branched alkoxy groups having 1 to 4 carbon atoms (as mentioned above), wherein in these groups partially or completely the hydrogen atoms may be replaced by halogen atoms as mentioned above, such as (but not limited to) Ci-C 2 -haloalkoxy as Chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2, 2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro, 2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloro
  • Thioalkyl saturated, straight-chain or branched alkylthio radicals having 1 to 6 carbon atoms, such as (but not limited to) C 1 -C 6 -alkylthio, such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio , 1,1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-
  • Cycloalkyl mono-, bi- or tricyclic, saturated hydrocarbon groups having 3 to 12 carbon ring members, such as e.g. (but not limited to) cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, bicyclo [l, o, l] butane, decalinyl norbornyl;
  • Cylcoalkenyl mono-, bi- or tricyclic non-aromatic hydrocarbon groups having 5 to 15 carbon ring members having at least one double bond, such as, but not limited to, cyclopenten-1-yl, cyclohexen-1-yl, cyclohepta-1,3-diene -l-yl, norbornen-1-yl;
  • Alkylcarbonyl an alkyl group having 1 to 4 carbon atoms (as mentioned above) which is bonded to the skeleton via a carbonyl group (-CO-);
  • Alkoxy carbonyl an alkoxy group having 1 to 4 carbon atoms (as mentioned above) which is bonded to the skeleton via a carbonyl group (-CO-);
  • Haloalkylcarbonyl a haloalkyl group having 1 to 4 carbon atoms (as mentioned above) which is linked to the skeleton via a carbonyl group (-CO-);
  • Arylalkyl an aryl group (as mentioned above) attached to the skeleton via an alkyl group (as mentioned above) such as, but not limited to, benzyl, 1-phenylethyl, 2-phenylethyl;
  • Aryloxy an aryl group (as mentioned above) which is linked to the skeleton via an oxygen atom;
  • Heterocycle three- to fifteen-membered saturated or partially unsaturated heterocycle containing one to four heteroatoms from the group consisting of oxygen, nitrogen or sulfur: mono-, bi- or tricyclic heterocycles containing, in addition to carbon ring members, one to three nitrogen atoms and / or one oxygen atom or one or more nitrogen atoms Sulfur atom or one or two oxygen and / or sulfur atoms; if the ring contains several oxygen atoms, these are not directly adjacent; such as, but not limited to, oxiranyl, aziridinyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3
  • 5-membered hetaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom 5-membered heteroaryl groups which may contain, in addition to carbon atoms, one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members. eg 2-furyl, 3-furyl, 2
  • benzo-fused 5-membered hetaryl containing one to three nitrogen atoms or a nitrogen atom and an oxygen or sulfur atom 5-membered heteroaryl groups which may contain, besides carbon atoms, one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members, and in which two adjacent carbon ring members or a nitrogen and an adjacent
  • Carbon ring member may be bridged by a buta-l, 3-diene-l, 4-diyl group in which one or two C atoms may be replaced by N atoms; e.g. Benzindolyl, benzimidazolyl, benzothiazolyl, benzopyrazolyl, benzofuryl;
  • 5-membered hetaryl bonded via nitrogen, containing one to four nitrogen atoms, or benzo-fused 5-membered heteroaryl bonded via nitrogen, containing one to three nitrogen atoms 5-membered heteroaryl groups which contain, in addition to carbon atoms, one to four nitrogen atoms or one to three nitrogen atoms may contain as ring members, and in which two adjacent carbon ring members or a nitrogen and an adjacent carbon ring member may be bridged by a buta-1,3-diene-1, 4-diyl group in which one or two C atoms are N atoms in which one or two C atoms may be replaced by N atoms, these rings being bonded to the skeleton via one of the nitrogen ring members, for example 1-pyrrolyl, 1-pyrazolyl, 1,2,4-triazole 1-yl, 1-imidazolyl, 1,2,3-triazol-1-yl, 1,3,4-triazol-1-yl; 6-membered hetaryl containing one
  • the compounds of formula (I) may have acidic or basic properties and may form salts with inorganic or organic acids or with bases or with metal ions, optionally also internal salts or adducts.
  • the metal ions are in particular the ions of the elements of the second main group, in particular calcium and magnesium, the third and fourth main group, in particular aluminum, tin and lead, and the first to eighth subgroup, in particular chromium, manganese, iron, cobalt, nickel, Copper, zinc and others into consideration. Particularly preferred are the metal ions of the elements of the fourth period.
  • the metals can be present in the various valences that belong to them.
  • Suitable bases are hydroxides, carbonates, bicarbonates of the alkali metals and alkaline earth metals, in particular those of sodium, potassium, magnesium and calcium, furthermore ammonia, primary, secondary and tertiary amines with (C 1 -C 4 ) -alkyl radicals, mono-, di- and trialkanolamines of (C 1 -C 4 ) -alkanols, choline and chlorocholine.
  • inorganic acids examples include hydrohalic acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, sulfuric acid, phosphoric acid and nitric acid and acid salts such as NaHSO 4 and KHSO 4 .
  • suitable organic acids are formic acid, carbonic acid and alkanoic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, Lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids having straight-chain or branched alkyl radicals having 1 to 20 carbon atoms), arylsulfonic acids or -disulfonic acids (aromatic radicals such as phenyl and naphthyl which carry one or two sulfonic acid groups), Alkylphosphonic acids (phosphonic acids having straight-chain or branched alkyl radicals having 1 to 20 carbon atoms), arylphosphonic acids or -diphosphonic acids (aromatic radicals such as phenyl and naphthyl which carry one or two phosphonic acid radicals),
  • the salts thus obtainable also have fungicidal and mycotoxin-reducing properties.
  • the 5-pyridin-4-yl (1,3-thiazoles) which can be used according to the invention can be prepared in a known manner (cf., WO99 / 21555, WO99 / 64418, JP05070446, WO01 / 30778, WO01 / 74811, WO02 / 062792, WO2000 / 64894, WO2001 / 10865, WO2007 / 077574, WO2006 / 137658, WO2004 / 089937, WO2005 / 063743, WO2007 / 076348, Chem. Pharm. Bull. 2005, 53, 410-418, J. Med. Chem. 2005, 48, 5966, /. Med. Chem. 2004, 47, 4494; Bioorg. Med. Chem. Lett., 2000, 10, 1261; Bioorg. Med. Chem. Lett., 2004, 14, 3595).
  • the invention also relates to compounds of the formula (Ia)
  • R la represents an optionally substituted by hydroxy, amino, cyano, halogen, OR 6, SR 6a, Ci-C4-haloalkoxy, R 5a, R 9a, Ci-C 4 alkylsulfinyl, C r C 4 alkylsulfonyl C r C 6- alkyl,
  • R 2a represents naphthyl, phenyl, phenyl which is monosubstituted or polysubstituted by fluorine, CF 3 or cyano, and 4-methylphenyl, 3,4-dimethylphenyl, 4-cyanophenyl, 3-cyanophenyl, 4-chlorophenyl,
  • thiophene radical which is optionally mono- or polysubstituted by identical or different radicals from the group halogen, cyano, Ci-C 4 alkyl, C r C 4 alkoxy, C r C 4 - haloalkyl;
  • R 5a is a phenyl radical which is optionally substituted with halogen, hydroxy, cyano, C C4alkyl, Ci-C 4 alkoxy, Ci-C2 haloalkoxy, Ci-C 2 haloalkyl, Ci-C 4 alkoxycarbonyl or carboxy is substituted;
  • R 6a is independently hydrogen, Ci-C 6 alkyl, optionally substituted with C 1 -C 4 - alkyl or halogen-substituted C 3 -C 6 cycloalkyl, QC ⁇ haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy (Ci-C 4) alkyl, hydroxy (C r C4) alkyl, AminoCd ⁇ alkyl,
  • two radicals R 6a are a 3 to 7-membered, unsubstituted or optionally mono- or polysubstituted, preferably up to three times by identical or different radicals from the group halogen, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -HaIOaIlCyI, C 1 -C 4 -alkoxy, C r C 4 -haloalkoxy, C 1 -C 4 -alkylcarbonyl or C 1 -C 4 -alkoxycarbonyl-substituted, saturated or unsaturated cycle, which may contain up to four further heteroatoms selected from N, O and S, wherein two oxygen atoms are not adjacent
  • two radicals R 63 is a 3 to 7-membered, unsubstituted or optionally mono- or polysubstituted, preferably up to three times by identical or different radicals from the group Halogen, Hydroxy, C 1 -C 4 -alkyl, C] -C 4 -HaIOaIlCyI, C 1 -C 4 -alkoxy or C 1 -C 4 -HaIOaIkOXy form substituted, saturated or unsaturated cycle which is selected up to four additional heteroatoms from N, O and S may contain, with two oxygen atoms are not adjacent
  • R 7a independently of one another are C 1 -C 6 -alkyl, a C 3 -C 6 -cycloalkyl optionally substituted by C 1 -C 4 -alkyl or halogen, C 1 -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 - alkynyl, C 1 -C 4 alkoxy (C 1 -C 4) alkyl, hydroxy (CrC 4) alkyl,
  • R 9a is a 3- to 7-membered, unsubstituted or optionally mono- or polysubstituted by identical or different radicals from the group Ci-C 4 alkyl, halogen, cyano, CpC 4 - haloalkyl or Cj-C 4 -Akoxy substituted, saturated , or partially unsaturated carbocycle,
  • R Ua is a five- or six-membered heteroaromatic which may contain up to three heteroatoms selected from N, O and S, where two oxygen atoms are not adjacent and optionally substituted with halo, cyano, C 1 -C 4 -alkyl, C r is C 4 -alkoxy, C 1 -C 2 -haloalkyl, C 1 -C 4 -alkoxycarbonyl,
  • n 1 and 6
  • R la is ethyl
  • R 2a for 3-trifluoromethylphenyl, thiophen-2-yl and 4-fluoro-3-methylphenyl
  • R 3a is NH 2 , NHAc, NHCOEt, NHCOPh
  • R Ia is ethyl
  • R 2a is phenyl or 4-chlorophenyl
  • R 3a represents hydrogen, NH 2 , NHAc, NHCOEt, NHCOPh, NHCOCH 2 Ph, NHCOCH 2 cPen, or NHCOO / Bu as well as compounds in which
  • R Ia is ethyl
  • R 3a is amino, NHAc, NHCOEt, NHCOCH 2 Ph
  • R la is ethyl
  • R 2a represents 4-methylphenyl or 3-cyanophenyl
  • R 3a is hydrogen, amino, NHCOPh, or NHCOCH 2 Ph
  • R la is ethyl
  • R 2a for 4-fluorophenyl
  • R 3a is amino, NHAc, NHCOEt, NHCOPh, NHCOCH 2 Ph, NHcHex, or fluorine.
  • the compounds of the invention are generally defined by the formula (Ia). Preferred radical definitions of the above and below formulas are given below. These definitions apply equally to the end products of formula (Ia) as well as to all intermediates.
  • R la for Ci-C 6 alkyl, a substituted with cyano or R 9a C r C 4 alkyl, optionally substituted with Ci-C 2 alkyl or halogen, C 3 -C 5 -CyClOaIlCyI, Ci-C 4 - Haloalkyl, Ci-C 4 - Alkyloxy (Ci-C 4 ) alkyl, hydroxy (C r C 4 ) alkyl, if necessary with halogen, methyl or
  • R 2a is naphthyl, phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,5-difluorophenyl, 2,4-
  • thiophene radical which is optionally mono- or polysubstituted by identical or different radicals from the group halogen, cyano, Ci-C 2 alkyl, Ci-C 2 alkoxy, C 1 -C 2 - haloalkyl;
  • R 3a is hydrogen, halogen, cyano, C r C 4 alkyl, COO (C r C 4 alkyl), CON (Ci -C 4 alkyl) 2, CONH (C 1 -C 4 -alkyl), CONH ( C 3 -C 6 -cycloalkyl), CONH (C 3 -C 6 -alkenyl), CONH (C 3 -C 6 -alkynyl), (CH 2 ) m CN, (CH 2 ) m NHCO (C r C 4 - Alkyl), (CH 2 ) m N (C 1 -C 4 -alkyl) CO (C 1 -C 4 -alkyl), (0 ⁇ ) ⁇ 3 ⁇ 6 ⁇ 010311 ⁇ 1) 00 (0, ⁇ 4 - / ⁇ 1), (CH 2 ) m N (C 3 -C 6 -alkenyl) CO (C 1 -C 4 -alkyl), (CH 2 )
  • Cycloalkyl NH (C r C 4 haloalkyl), NH (C 3 -C 6 alkenyl), NH (C 3 -C 6 alkynyl), NHCH (Me) CH 2 OMe, NHCH (Me) CH 2 OH , NHCH 2 CH (Me) OMe, NHCH 2 CH (Me) OH,
  • NHCOH NHCOH, NHCO (C r C 6 alkyl), NHCO (CH 2 ) m O (C r C 4 alkyl), NHCOCHMeOMe, NHCO (C, C 4 haloalkyl), NHCOCHMeOH, NHCOCHMeNH 2 , NHCOCH 2 NH 2 .
  • NHCOC C 2 -C 6 alkenyl
  • Ntd-Q-alkyl ⁇ CO ⁇ rQ alkenyl N (C 3 -C 6 cycloalkyl) CO (C 2 -C 6 alkenyl), N (C 3 - C 6 -alkenyl) CO (C 2 -C 6 -alkenyl), N (C 3 -C 6 -alkynyl) CO (C 2 -C 6 -alkenyl),
  • NHCOR 5 NHCO (CH 2) ,, ⁇ 3, NHCOR 113, N (C r C 4 alkyl) COR 5, N (C 3 -C 6 alkenyl) COR 5a, N (C 3 -C 6 alkynyl ) COR 5a ,
  • R 5a represents a phenyl radical which is optionally mono- or polysubstituted by identical or different radicals from the group consisting of methyl, fluorine, chlorine, methoxy, or cyano
  • R 9a represents a saturated or saturated 3 to 6 membered, unsubstituted or mono- or polysubstituted by identical or different radicals from the group methyl, fluorine, chlorine, cyano,
  • R lla is a heteroaromatic radical selected from the group consisting of furan, thiophene, pyridine or pyrazine and optionally substituted by fluorine, chlorine, cyano, methyl, OMe;
  • n 1 and 4
  • R la is ethyl
  • R 2a for 3-trifluoromethylphenyl, thiophen-2-yl and 4-fluoro-3-methylphenyl
  • R 3a is NH 2 , NHAc, NHCOEt, NHCOPh
  • R la is ethyl
  • R 2a is phenyl or 4-chlorophenyl
  • R 3a is hydrogen, NH 2 , NHAc, NHCOEt, NHCOPh, NHCOCH 2 Ph, NHCOCH 2 cPen or NHCOOiBu;
  • R la is ethyl
  • R 3a is amino, NHAc, NHCOEt, NHCOCH 2 Ph
  • R la is ethyl
  • R 28 is 4-methylphenyl or 3-cyanophenyl
  • R 3a represents hydrogen, amino, NHCOPh, or NHCOCH 2 Ph
  • R la is ethyl
  • R 3a is amino, NHAc, NHCOEt, NHCOPh, NHCOCH 2 Ph, NHcHex, or fluorine.
  • R la is methyl, ethyl, 1-methylethyl, propyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 Ethylpropyl,
  • Cyclopropyl 1-methylcyclopropyl, 2-methylcyclopropyl, 1-chlorocyclopropyl, 2-chlorocyclopropyl, cyclobutyl, cyclopentyl, (cyclopropyl) methyl
  • R 2a is phenyl, 2-fluo ⁇ henyl, 3-fluo ⁇ henyl, 4-Fluo ⁇ henyl, 2,5-Difluo ⁇ henyl, 2,4-Difluo ⁇ henyl, 2,6-Difluo ⁇ henyl, 2,4,6-trifluorophenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl , 4-methylphenyl, 3,4-dimethylphenyl, 4-cyanophenyl, 3-cyanophenyl, 4-chlorophenyl, 4-fluoro-3-methylphenyl, 3-cyano-4-fluorophenyl,
  • NHCSMe NHCSEt
  • NHCSzPr NHCScPr
  • NHCSPh NHCSMe, NHCSEt, NHCSzPr, NHCScPr, NHCSPh
  • R la is ethyl
  • R 2a for 3-trifluoromethylphenyl, thiophen-2-yl and 4-fluoro-3-methylphenyl
  • R 3a is NH 2 , NHAc, NHCOEt, NHCOPh;
  • R la is ethyl
  • R 2a is phenyl or 4-chlorophenyl
  • R 3a is hydrogen, NH 2 , NHAc, NHCOEt, NHCOPh, NHCOCH 2 Ph, or NHCOOfBu; as well as compounds in which
  • R la is ethyl
  • R 3a is amino, NHAc, NHCOEt, NHCOCH 2 Ph;
  • R la is ethyl
  • R 2a represents 4-methylphenyl or 3-cyanophenyl
  • R 3a represents hydrogen, amino, NHCOPh, or NHCOCH 2 Ph
  • R la is ethyl
  • R 2a for 4-fluorophenyl
  • R 3a is amino, NHAc, NHCOEt, NHCOPh, NHCOCH 2 Ph, or fluorine.
  • R la is methyl, ethyl, 1-methylethyl, butyl, 1,1-dimethylethyl, cyclopropyl, difluoromethyl, benzyl,
  • R 2a represents phenyl, 4-fluorophenyl, 3-trifluoromethylphenyl, 3,4-dimethylphenyl,
  • R 3a represents hydrogen, fluorine, chlorine, methyl, CON (Me) Et, CONHcPr,
  • NHAc, NHCOEt, NHCOPr, NHCO / Pr, NHCOiBu, NHCOsecBu, NHCOJ-BU, NHCOCH 2 OMe, NHCOCH 2 Cl, NHCOcPr, (1-methylcyclopropylcarbonyamino, (2-methylcyclopropylcarbonyl) amino, NHCOcBu, NHCOcHex, NHCOC (Me) CH 2 ,
  • R la is ethyl
  • R 3a is NH 2 , NHAc, NHCOEt, NHCOPh
  • R la is ethyl
  • R 2a is phenyl
  • R 3a is hydrogen, NH 2 , NHAc, NHCOEt, NHCOPh, NHCOCH 2 Ph, or NHCOOfBu
  • R la is ethyl
  • R 2a for 4-fluorophenyl
  • R 3a is amino, NHAc, NHCOEt, NHCOPh, NHCOCH 2 Ph or fluorine.
  • R 2a is phenyl, 4-methylphenyl, 4-fluorophenyl and 4-chlorophenyl, where the other substituents have one or more of the meanings mentioned above, and the agrochemically active salts thereof.
  • R 2a is a thiophene radical which is optionally mono- or polysubstituted by identical or different radicals from the group consisting of halogen, cyano, C 1 -C 2 -alkyl, C 1 -C 2 -alkoxy C 1 -C 2 haloalkyl is substituted; very particular preference is given to thiophen-2-yl, 5-chlorothiophen-2-yl, thiophen-3-yl, 5-methylthiophen-3-yl; wherein the other substituents have one or more of the meanings mentioned above, and the agrochemically active salts thereof.
  • R la represents C 1 -C 4 -alkyl, Ci-C 4 - haloalkyl or C 3 -C 5 -Cyclalkyl, wherein the other substituents have one or more of the abovementioned meanings and the agrochemically active salts thereof.
  • R 3a is NR 63 COR 53 , NR 63 COR 1 la , where the other substituents have one or more of the meanings mentioned above, and the agrochemically active salts thereof.
  • R 3a is NR 63 COR 63 , NR 63 COR 93 , NR 6a CO (CH 2 ) m R 9a , where the other substituents have one or more of the meanings mentioned above, and the agrochemically active salts thereof.
  • the pyridinylthiazoles of the general formula (Ia) according to the invention can be prepared in various ways, as shown schematically below. Unless otherwise indicated, the radicals indicated have the meanings given above.
  • the pyridinylthiazoles of the general formula (Ia) according to the invention can be prepared by process A according to the following scheme (scheme A):
  • (VIII) is formed either in a step [V4] in the presence of hydrogen sulfide or alternatively in a step [V5] in the presence of P 4 S 10 or Lawesson's reagent, to the compounds of formula (Ia) according to claim 1 according to the invention.
  • LG is selected from the group alkoxy, cyano, dialkylamino, N (alkyl) -Oalkyl, LG is preferably methoxy, ethoxy and N (Me) OMe;
  • Hal 1 is selected from the group chlorine, bromine, iodine.
  • R 1a , R 2a and R 3a are generally, preferably, more preferably and most preferably those meanings which have already been mentioned in connection with the description of the compounds of the formula (Ia) according to the invention as being preferred, particularly preferred or very particularly preferred for these radicals.
  • Compounds of the general formula (TV) are either commercially available or can be prepared by condensation of 4-methylpyridines of the general formula (H) with compounds of the general formula R 2a CO-LG (HI) in the presence of a base.
  • 4-Methylpyridines of the general formula (H) are either commercially available or can be prepared, for example, from the corresponding 4-halopyridines (for example analogously Chemistry-Eur. J. 2009, 15, 4165-4171; Tetrahedron 1997, 53, 13749-13756; Org. Chem. 1985, 50, 5405-9).
  • Carboxylic acid derivatives of the general formula (HI) are commercially available or can be prepared by conventional methods of organic synthesis from the analogous carboxylic acids.
  • Halogenation allows the compounds of general formula (V) to be obtained from compound (IV).
  • the subsequent conversion Substitution of compounds of the formula (V) with thiamides of the general formula (VI) gives the inventive pyridinylthiazoles of the formula (Ia).
  • the thiamides of the general formula (VI) used are either commercially available or can be prepared by literature methods from the nitriles of the formula (VII) or from the carboxamides of the formula (VHI).
  • Suitable bases for carrying out process step VI of Scheme A are alkali metal alkoxides (e.g., KOtBu, NaOtBu), lithium amides (e.g., sodium amide lithium diisopropylamide, lithium bis (trimethylsilyl) amide) or metal hydrides (e.g., KH, NaH).
  • alkali metal alkoxides e.g., KOtBu, NaOtBu
  • lithium amides e.g., sodium amide lithium diisopropylamide, lithium bis (trimethylsilyl) amide
  • metal hydrides e.g., KH, NaH
  • cyclic and acyclic ethers e.g., diethyl ether, tetrahydrofuran, dimethoxyethane
  • amides e.g., dimethylformamide, dimethylacetamide
  • the reaction temperature is for carrying out the process step Vl of Scheme A between -78 ° C and the boiling point of the solvent, preferably between -78 0 C and room temperature.
  • reaction time for carrying out the process step VI according to the invention from Scheme A is between 5 minutes and 24 hours, preferably between 30 minutes and 3 hours, depending on the scale of the reaction.
  • Carboxylic acid derivatives of the general formula (III) are commercially available or can be prepared by conventional methods of organic synthesis from the analogous carboxylic acids.
  • halogenating reagents such as elemental chlorine, bromine, iodine or N-halo-succinimides (NCS, NBS, NIS) or sulfuryl chloride and pyridinium tribromide
  • the halogenation for carrying out the process step V2 according to the invention from Scheme A can be carried out in the presence of a solvent which is inert under the reaction conditions.
  • alcohols for example methanol, ethanol
  • cyclic and acyclic ethers for example diethyl ether, tetrahydrofuran, dioxane
  • amides for example dimethylformamide, dimethylacetamide
  • sulphoxides for example dimethyl sulphoxide
  • aromatic hydrocarbons for example benzene, toluene
  • halogenated hydrocarbons for example, dichloromethane, chloroform
  • carboxylic acids eg, acetic acid
  • the reaction temperature for carrying out the process step V2 according to the invention is between 0 0 C and the boiling point of the solvent, preferably between room temperature and 80 0 C.
  • the reaction time for carrying out the process step V2 invention is dependence on the scale of reaction between 5 min and 24 h in the absence , preferably between 30 minutes and 6 hours.
  • alkali metal carbonates eg sodium potassium, cesium carbonate, sodium bicarbonate
  • alkali metal phosphates eg disodium hydrogen phosphate
  • aromatic amines eg pyridine, lutidine
  • tertiary amines triethylamine, ethyldiisopropylamine, N-methylpiperidine , N-methylmorhpholine
  • Suitable solvents for carrying out process step V3 according to the invention from Scheme are all solvents and mixtures thereof which are inert under the reaction conditions.
  • Preferred are alcohols (e.g., methanol, ethanol), cyclic and acyclic ethers (e.g., diethyl ether, tetrahydrofuran, dimethoxyethane), amides (e.g., dimethylformamide, dimethylacetamide), sulfoxides (e.g., dimethylsulfoxide), and nitriles (e.g., acetonitrile).
  • alcohols e.g., methanol, ethanol
  • cyclic and acyclic ethers e.g., diethyl ether, tetrahydrofuran, dimethoxyethane
  • amides e.g., dimethylformamide, dimethylacetamide
  • sulfoxides e.g., dimethylsulfoxide
  • the reaction temperature for carrying out the process step V3 according to the invention from Scheme is between 0 ° C and the boiling point of the solvent, preferably between room temperature and 100 0 C.
  • the reaction time for carrying out the process step V3 according to the invention of scheme is depending on the scale of the reaction between 5 min and 72 h, preferably between 30 min and 24 h.
  • the thiamides of the general formula (VI) used are either commercially available or can be prepared by methods known from the literature, e.g. by reacting a nitrile (VII) with hydrogen sulfide, if appropriate in the presence of a suitable base (for example triethylamine, described in Tetrahedron, 1989, 45, 7329-40) and a suitable solvent (for example chloroform, dimethylformamide, pyridine, methanol, ethanol) or by thionation of a carboxamide (Vm) using phosphorus pentasulfide (see WO2007 / 039177) or Lawesson's reagent (see Tetrahedron, 1985, 41, 2567-624) in the presence of a suitable solvent such as benzene, toluene, pyridine, tetrahydrofuran or dioxane.
  • a suitable base for example triethylamine, described in Tetrahedron, 1989, 45, 7329-40
  • pyridinylthiazoles of the general formula (Ia) according to the invention can also be prepared by process B (scheme B):
  • Met 1 B (OH) 2 or 4,4,5,5-tetramethyl-l, 3,2-dioxaborolan-2-yl.
  • Hal 1 stands for Cl, Br, I.
  • these 5-H-thiazoles (X) may be selective at first at the 5-position to give compounds of formula (XI) and subsequently in a Suzuki Stille reaction with pyridines of general formula (XIII) to the desired pyridinylthiazoles of the formula (Ia) are implemented. It is likewise possible to prepare from compounds of the formula (X) the boronic acid or esters of the formula (XV) and to convert them in a Suzuki reaction with A-bromopyridines of the formula (XS) into compounds of the formula (Ia).
  • 5-H-thiazoles of the general formula (X) are obtainable by reaction of thiamides of the general formula (VI) with halomethylcarbonylene of the general formula (IX) analogously to process step [V3] from process A (described, for example, in J. Med. Chem 2008, 51, 6110-6120).
  • the halomethylcarbonyls (IX) are either commercially available or may be prepared by suitable halogenating agents (e.g., bromine, NBS, NCS) from appropriate acetophenones (see Synthesis, 2008, 253-266) or by Friedel-Crafts acylation with e.g. Chloroacetic acid chloride (see J. Org. Chem. 1985, 50, 5612-15) from the corresponding (Het-) aromatics win.
  • the 5-H-thiazoles of the general formula (X) can be Pd-catalyzed with 4-bromopyridines of the general formula (Xu) in the presence of a suitable base to give the pyridinylthiazoles (Ia) according to J. Org. Chem., 2009, 74, 1179-86.
  • palladium catalysts in which the palladium is in the oxidation state (0) or (II), e.g. Tetrakis (triphenylphosphine) palladium, bis (dibenzylideneacetone) palladium, palladium (II) acetate, palladium (II) chloride.
  • (0) or (II) e.g. Tetrakis (triphenylphosphine) palladium, bis (dibenzylideneacetone) palladium, palladium (II) acetate, palladium (II) chloride.
  • the catalyst for carrying out process step V7 of the invention from Scheme B may contain phosphorus-containing ligands, or phosphorus-containing ligands may be added separately to the reaction mixture.
  • Suitable phosphorus-containing ligands are preferably tri-n-alkylphosphines, triarylphosphines, dialkylarylphosphines, alkyldiarylphosphanes and / or heteroarylphosphines, such as tripyridylphosphine and trifurylphosphane, where the three substituents on the phosphor may be identical or different and where one or more substituents are phosphorus - groups of several phosphenes can link.
  • Particularly preferred are phosphines such as triphenylphosphine, tri-tert-butylphosphane, tricyclohexylphosphane.
  • Suitable bases for carrying out the process step V7 according to the invention from Scheme B are alkali metal carbonates (for example K 2 CO 3 ), alkali metal acetates (for example KOAc), and tertiary amines (for example triethylamine).
  • alkali metal carbonates for example K 2 CO 3
  • alkali metal acetates for example KOAc
  • tertiary amines for example triethylamine
  • Suitable solvents for carrying out the process step V7 according to the invention from Scheme B for the Heck reaction are all customary solvents which are inert under the reaction conditions, such as cyclic and acyclic ethers (dimethoxymethane, tetrahydrofuran, dioxane), aromatic hydrocarbons (eg toluene), nitriles (eg acetonitrile , Propionitrile,) and amides (eg, dimethylformamide, dimethylacetamide, N-methylpyrrolidone), or the reaction can be carried out in mixtures of two or more of these solvents.
  • cyclic and acyclic ethers diimethoxymethane, tetrahydrofuran, dioxane
  • aromatic hydrocarbons eg toluene
  • nitriles eg acetonitrile , Propionitrile,
  • amides eg, dimethylformamide, dimethylacetamide, N-methylpyr
  • the reaction temperature for carrying out the process step V7 invention from Scheme B is between 50-150 0 C and the -time between 3 h and 24 h.
  • Suitable solvents for the Suzuki reaction can be any of the usual inert solvents under the reaction conditions, such as alcohols (e.g., ethanol, ethylene glycol), cyclic and acyclic ethers
  • Suitable bases for carrying out the process step V9 of Scheme B are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal acetates, alkali metal alcoholates, and tertiary amines.
  • Preferred bases are cesium carbonate, sodium carbonate, potassium carbonate or potassium acetate.
  • Preferred for carrying out the process step V9 according to the invention are palladium catalysts in which the palladium in the oxidation state (0) or (II) is present, such. Tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride and bis (diphenylphosphino) ferrocenepalladium dichloride or also palladium (II) acetate and palladium (II) chloride.
  • the catalyst for carrying out the process step V9 according to the invention may contain phosphorus-containing ligands or phosphorus-containing ligands may be added separately to the reaction mixture.
  • Preferred phosphorus-containing ligands are tri-n-alkylphosphines, triarylphosphines, dialkylarylphosphanes, alkyldiarylphosphanes and / or heteroarylphosphines, such as tri-pyridylphosphane and trifurylphosphane, where the three substituents on the phosphorus may be identical or different and where one or more substituents are the phosphorus groups can link several phosphines, wherein a part of this linkage can also be a metal atom.
  • Particularly preferred are phosphines such as triphenylphosphine, tri-tert-butylphosphane, tricyclohexylphosphine.
  • the Suzuki coupling in the implementation of the process step V9 according to the invention is carried out in a temperature range of 25 ° to 200 0 C, more preferably at 80 ° to 150 0 C.
  • the reaction time for carrying out the process step V9 according to the invention varies depending on the scale of the reaction and the reaction temperature, but is generally between a few minutes and 48 hours.
  • the preparation of 4-pyridinylstannanes (XIII) is likewise known from the literature (for example J. Med. Chem. 2003, 46, 284-302, Tetrahedron 2004, 60, 6113-6120).
  • the selection of a catalyst, optionally an inorganic or organic halide salt, optionally a ligand and a suitable solvent at suitable temperatures vary depending on the Zinnal- kyl substrate used.
  • Suitable solvents for the Stille coupling are all customary solvents which are inert under the reaction conditions, such as cyclic and acyclic ethers (for example dimethoxymethane, tetrahydrofuran, dioxane,), aromatic hydrocarbons (for example toluene), amides (for example dimethylformamide, dimethy - lacetamide, N-methylpyrrolidone) and sulfoxides (eg dimethylsulfoxide) or the reaction can be carried out in mixtures of two or more of these solvents.
  • cyclic and acyclic ethers for example dimethoxymethane, tetrahydrofuran, dioxane,
  • aromatic hydrocarbons for example toluene
  • amides for example dimethylformamide, dimethy - lacetamide, N-methylpyrrolidone
  • sulfoxides eg dimethylsulfoxide
  • Halide salts which are preferably used are e.g. Copper halides (e.g., CuBr or CuI), cesium halides (e.g., CsF), and tetraalkylammonium halides (e.g., TBAF).
  • Copper halides e.g., CuBr or CuI
  • cesium halides e.g., CsF
  • tetraalkylammonium halides e.g., TBAF
  • palladium catalysts in which the palladium is in the oxidation state (0) or (IT), e.g. Tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride and bis (diphenylphosphino) ferrocenepalladium dichloride or else palladium (II) acetate and palladium ( ⁇ ) chloride.
  • the catalyst may contain phosphorus-containing ligands or phosphorus-containing ligands may be added separately to the reaction mixture.
  • Suitable phosphorus-containing ligands are preferably tri-n-alkylphosphines, triarylphosphines, dialkylarylphosphines, alkyldiarylphosphanes and / or heteroarylphosphines, such as tripyridylphosphine and trifurylphosphine, where the three substituents on the phosphorus may be identical or different and where one or more substituents are the phosphorus groups can connect a plurality of phosphenes, wherein a part of this linkage can also be a metal atom.
  • Particularly preferred are phosphines such as triphenylphosphine, tri-tert-butylphosphane, tricyclohexylphosphane.
  • the Stille coupling is carried out in a temperature range of 25 ° - 200 0 C, more preferably at 60 ° - 150 0 C.
  • the reaction time varies depending on the scale of the reaction and the reaction temperature, but is generally between a few minutes and 48 hours.
  • process C pyridinylthiazoles of the general formula (Ic to Ij)
  • Z 1 is N (R 6a ) 2 , preferably NHBn, NHfBn or a primary amine.
  • Z 2 is R'CO, R "COO and R '" SO 2 , where R' is R 5a , R 6a , R 9a and R lla , R "is R 7a , R '" is R 5a and R 6a , Z 3 is N (R 6a ) 2 and OR 6a .
  • Hal 2 is chlorine and bromine, LG is halogen, hydroxy and OZ 2 .
  • R 1a , R 2a , R 5a , R 6a , R 9a and R l la generally, preferably, more preferably or very particularly preferably those meanings which already in connection with the description of the inventive compounds of formula (Ia) as preferred, particularly preferred or very particularly preferred for these Remainders were specified.
  • the halogen atom can be further exchanged by N-nucleophiles to give compounds of the general formula (Ie) receives.
  • Z 1 NHBn or NHtBu
  • the benzyl or / Bu radical can be selectively removed in an acidic medium to give (2-aminopyridin-4-yl) thiazoles (If).
  • compounds of the general formula (If) can also be prepared by literature methods (J. Med. Chem, 2005, 48, 5966-5979) according to process A starting from tert-butyl (4-methylpyridin-2-yl) carbamate ,
  • 2-cyano-pyridines (Ii) can be obtained from the N-oxides. Subsequent catalytic hydrogenation of the cyano function allows acylation with Z 2 -LG of the amino function and gives compounds of general formula (Ij).
  • Suitable oxidizing agents for carrying out process step V12 according to the invention from scheme C are hydrogen peroxide, hydrogen peroxide with catalytic amounts of methyltrioxorhenium, peracids (for example m-chloroperoxybenzoic acid) or dimethyldioxirane.
  • the oxidations are optionally carried out in halogenated hydrocarbons (e.g., dichloromethane), amides (e.g., dimethylformamide), ketones (e.g., acetone), nitriles (e.g., acetonitrile), or acids (acetic acid) as a solvent.
  • N-oxide formation for carrying out the process step Vl of the invention 2 of Scheme C is performed in a temperature range of 0 ° to 110 0 C.
  • the reaction time varies depending on the scale of the reaction and the reaction temperature, but is generally between a few minutes and 24 hours.
  • a base for example triethylamine
  • suitable solvents for process step [V13] the halogenating reagents themselves or else, for example, halogenated hydrocarbons (eg 1,2-dichloroethane) or aromatic hydrocarbons (eg toluene) can be used.
  • the halogenation for carrying out the erf ⁇ ndungshielen process step Vl 3 from Scheme C is carried out in a temperature range of 25 ° to 150 0 C.
  • the reaction time for carrying out process step V13 of Scheme C according to the invention varies depending on the scale of the reaction and the reaction temperature, but is generally between a few minutes and 24 hours.
  • process step [V 14] One possibility for the preparation of compounds of the general formula (Ie) is described by process step [V 14].
  • the halogen atoms from (Id) are substituted by appropriate primary or secondary amines HN (R 6a ) 2 optionally in the presence of a base and optionally in the presence of a solvent.
  • the amines themselves or all conventional solvents which are inert under the reaction conditions, such as cyclic and acyclic ethers (dimethoxymethane, tetrahydrofuran, dioxane), aromatic hydrocarbons (eg Toluene), nitriles (eg acetonitrile, propionitrile,) and amides (eg dimethylformamide, dimethylacetamide, N-methylpyrrolidone) or the reaction can be carried out in mixtures of two or more of these solvents.
  • the preferred solvents are dimethylformamide or acetonitrile.
  • Suitable bases for carrying out the process step V14 according to the invention from Scheme C are alkali metal hydroxides, alkali metal hydrides, alkali metal carbonates, alkali metal acetates, alkali metal alcoholates and tertiary amines.
  • Preferred bases are sodium hydride, sodium carbonate, potassium carbonate or cesium carbonate.
  • the reaction temperature for carrying out the process step V14 from Scheme C according to the invention is between 0 ° C. and 180 ° C., preferably between room temperature and 100 ° C. Reaction can be carried out under normal pressure or under pressure.
  • the reaction time, depending on the scale of the reaction, is between 5 minutes and 24 hours, preferably between 30 minutes and 6 hours.
  • Suitable acids for this purpose are mineral acids (eg H 2 SO 4 , HCl,) Lewis acids (eg BBr 3 , AlCl 3 ) or organic acids (eg F 3 COOH, CF 3 SO 3 H).
  • the solvents used are the acids themselves or all customary solvents which are inert under the reaction conditions, such as halogenated hydrocarbons (for example dichloromethane) or aromatic hydrocarbons (for example toluene).
  • the reaction temperature is between 0 0 C and 100 0 C.
  • the reaction time is depending on the scale of the reaction between 5 min and 24 h, preferably between 30 min and 12 h.
  • solvents for carrying out the process step Vl 6 and Vl 7 from Scheme C according to the invention it is possible to use all customary solvents which are inert under the reaction conditions, e.g. cyclic and acyclic ethers (eg tetrahydrofuran, dioxanes), aromatic hydrocarbons (eg toluene), halogenated hydrocarbons (eg dichloromethane), ketones (eg acetone), amides (eg dimethylformaid) and nitriles (eg acetonitrile) are used or the reaction may be carried out in mixtures of two or more of these solvents.
  • the preferred solvents are tetrahydrofuran, dichloromethane and acetonitrile.
  • Suitable acid scavengers for carrying out the process step Vl 6 and Vl 7 from Scheme C according to the invention may be suitable bases.
  • Vl 6 and Vl 7 from Scheme C is normally carried out at temperatures of 0 0 C - 100 0 C and preferably at room temperature, but it can also be carried out to the reflux temperature of the reaction mixture.
  • the reaction time varies depending on the scale of the reaction and the reaction temperature, but is generally between a few minutes and 48 hours.
  • Suitable coupling reagents for carrying out the process step Vl 6 and V17 of Scheme C are, for example, carbodiimides (eg N- (3-dimethylaminopropyl) -N'-ethyl-carbodiimide optionally with 4-dimethylaminopyridine or 1-hydroxybenzotriazole) phosphonium ions (eg Bromo-tripyrrolidino-phosphonium hexafluorophosphate) or uronium ions (eg 0- (7-azabenzotriazol-1-yl) -N, N, N ', N'-tetramethyl-uronium hexa-fluorophosphate).
  • carbodiimides eg N- (3-dimethylaminopropyl) -N'-ethyl-carbodiimide optionally with 4-dimethylaminopyridine or 1-hydroxybenzotriazole
  • phosphonium ions eg Bromo-tripyrroli
  • a base for carrying out the process step Vl 6 and V17 according to the invention from Scheme C such as e.g. Triethylamine or ethyldiisopropylamine be used in the reaction.
  • a solvent for carrying out the process step Vl 6 and VII of the invention from Scheme C it is possible to use all customary solvents which are inert under the reaction conditions, as described for the reaction with acid chlorides.
  • the alcohols or the amines themselves and, moreover, all customary solvents which are inert under the reaction conditions, such as cyclic and acyclic ethers (eg dioxane), aromatic hydrocarbons (eg toluene), Sulfoxides (eg DMSO) and amides (eg dimethylformamide, dimethylacetamide, N-methylpyrrolidone) can be used or the reaction can be carried out in mixtures of two or more of these solvents.
  • the preferred solvents are the alcohols or the amines themselves and dimethylformamide.
  • Suitable bases for carrying out process step Vl 9 of Scheme C are alkali metal carbonates (e.g., potassium carbonate), cyclic amidines (e.g., DBU), and tertiary amine (e.g., triethylamine).
  • alkali metal carbonates e.g., potassium carbonate
  • cyclic amidines e.g., DBU
  • tertiary amine e.g., triethylamine
  • Preferred for carrying out the inventive method step Vl 9 from Scheme C are palladium catalysts in which the palladium in the oxidation state (0) or (U) is present, such as. Tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride, bis (diphenylphosphino) ferrocenepalladium dichloride and palladium (II) acetate.
  • the catalyst may contain phosphorus-containing ligands or phosphorus-containing ligands may be added separately to the reaction mixture.
  • Suitable phosphorus-containing ligands are preferably tri-n-alkylphosphines, triarylphosphines, dialkylarylphosphines, alkyldiarylphosphanes where the three substituents on the phosphorus may be identical or different and where one or more substituents may link the phosphorous groups of several phosphanes, a portion of this linkage may also be a metal atom.
  • Particularly preferred are phosphines such as triphenylphosphine and 1,4-bis (diphenylphosphino) propane and l, l'-bis (diphenylphosphino) ferrocenes.
  • the reaction for carrying out the inventive method step Vl 9 from Scheme C is carried out in a temperature range of 25 ° to 150 0 C, more preferably at 80 ° to 120 0 C.
  • the reaction can be carried out under normal pressure or under pressure.
  • the reaction time varies depending on the scale of the reaction and the reaction temperature, but is generally between a few minutes and 20 hours.
  • N-oxides of the general formula (Ic) are mixed with suitable cyanide sources (eg TMS-CN, NaCN), as described by way of example in WO2007 / 093542.
  • suitable cyanide sources eg TMS-CN, NaCN
  • an activator for example Dimethylcarbaminicchlorid, benzoyl chloride, dimethyl sulfate
  • an inert solvent such as dichloromethane, acetonitrile or dimethylformamide
  • process step [V21] a catalytic hydrogenation of the cyano function for the amino function allows acylation with Z 2 -LG analogous to process step [V 16] and compounds of the general formula (Ij) are obtained.
  • Palladium (eg Pd / C) or nickel (eg Raney Ni) can serve as hydrogenation catalysts for this purpose.
  • Suitable solvents for carrying out the process step V21 of Scheme C according to the invention are alcohols (for example methanol, ethanol) or carboxylic acids (for example acetic acid).
  • the reaction can be carried out under normal pressure or under pressure.
  • the reduction of the cyano function also by means of metal hydrides (eg LiAlH 4 in inert solvents such as tetrahydrofuran) at temperatures between 0 ° and 40 0 C.
  • R 1a and R 2a have the general, preferred, particularly preferred and most preferred meanings given above
  • R 1a has the general, preferred, particularly preferred and very particularly preferred meanings given above,
  • R 2a is phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,5-difluorophenyl, 2,4-difluorophenyl, 2,6-difluorophenyl, 2,4,6-trifluorophenyl, 3-trifluoromethylphenyl, 4-
  • Trifluoromethylphenyl 4-methylphenyl, 3,4-dimethylphenyl, 4-cyanophenyl, 3-cyanophenyl, 4-chlorophenyl, 3-methyl-4-fluorophenyl, 3-cyano-4-fluorophenyl or
  • thiophene radical which is optionally mono- or polysubstituted by identical or different radicals from the group halogen, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl;
  • Hal is chlorine, bromine iodine, preferably bromine, with the proviso that when
  • R 2a is phenyl, 4-chlorophenyl or 4-cyanophenyl
  • R la is not methyl, or bromomethyl.
  • the present invention further relates to a crop protection agent for controlling unwanted fungi and for the reduction of mycotoxins in plants and plant parts comprising at least one 5-pyridin-4yl (1,3) thiazole of the formula (I) and of the formula (Ia).
  • fungicidal and mycotoxin reducing agents containing agriculturally useful adjuvants, solvents, carriers, surfactants or diluents.
  • the invention relates to a method for controlling unwanted microorganisms, characterized in that according to the invention 5-pyridin-4yl (l, 3) thiazoles of the formula (I) and the formula (Ia) on the phytopathogenic and mycotoxin-producing fungi and / or their Habitat.
  • the carrier means a natural or synthetic, organic or inorganic substance, with which the active ingredients for better applicability, v. A. for application to plants or plant parts or seeds, mixed or combined.
  • the carrier which may be solid or liquid, is generally inert and should be useful in agriculture.
  • Suitable solid or liquid carriers are: for example, ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and natural or synthetic silicates, resins, waxes, solids Fertilizers, water, alcohols, especially butanol, organic solvents, mineral and vegetable oils and derivatives thereof. Mixtures of such carriers Substances can also be used.
  • ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth
  • ground synthetic minerals such as finely divided silica, alumina and natural or synthetic silicates, resins, waxes, solids Fertilizers, water, alcohols, especially butanol, organic solvents, mineral and vegetable oils and derivatives thereof. Mixtures of such carriers Substances can also be used.
  • solid carriers for granules are: for example, broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corncobs and tobacco stalks.
  • Suitable liquefied gaseous diluents or carriers are those liquids which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants, such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide.
  • Aerosol propellants such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex polymers may be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids.
  • Other additives may be mineral and vegetable oils.
  • Suitable liquid solvents are essentially: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or dichloromethane, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g.
  • Petroleum fractions mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • alcohols such as butanol or glycol and their ethers and esters
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone
  • strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • compositions of the invention may additionally contain other ingredients, such as surfactants.
  • Suitable surface-active substances are emulsifying and / or foam-forming agents, dispersants or wetting agents having ionic or nonionic properties or mixtures of these surface-active substances.
  • Examples thereof are salts of polyacrylic acid, salts of lignosulphonic acid, salts of phenolsulphonic acid or naphthalenesulphonic acid, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (preferably alkylphenols or arylphenols), salts of sulphosuccinic acid esters, taurine derivatives (preferably alkyltaurates ), Phosphoric acid esters of polyethoxylated alcohols or phenols, fatty acid esters of polyols, and derivatives of the compounds containing sulphates, sulphonates and phosphates, for example alkylarylpolyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates, protein hydrolysates, lignin-sulphite liquors and methylcellulose.
  • the presence of a surfactant is necessary when one of the active ingredients and / or one of the inert carriers is not soluble in water and when applied in water.
  • the proportion of surface-active substances is between 5 and 40 percent by weight of the agent according to the invention.
  • Dyes such as inorganic pigments such as 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.
  • additional components may also be included, e.g. protective colloids, binders, adhesives, thickeners, thixotropic substances, penetration promoters, stabilizers, sequestrants, complexing agents.
  • the active ingredients can be combined with any solid or liquid additive commonly used for formulation purposes.
  • the formulations generally contain between 0.01 and 99% by weight, 0.05 and 98% by weight, preferably between 0.1 and 95% by weight, particularly preferably between 0.5 and 90% of active ingredient, completely more preferably between 10 and 70 weight percent.
  • the active compounds or compositions according to the invention can be used as such or as a function of their physical and / or chemical properties in the form of their formulations or the use forms prepared therefrom, such as aerosols, capsule suspensions, cold mist concentrates, hot mist concentrates, encapsulated granules, fine granules, flowable concentrates for the treatment - Depended on seeds, ready to use solutions, dustable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, macrogranules, microgranules, oil dispersible powders, oil miscible flowable concentrates, oil miscible liquids, foams, pastes, pesticide coated seed, suspension concentrates, suspension emulsion concentrates, soluble concentrates, suspensions, wettable powders, soluble powders, dusts and granules, water-soluble granules or tablets, water-soluble powders for seed treatment, wettable powders, imp
  • the formulations mentioned can be prepared in a manner known per se, e.g. by mixing the active compounds with at least one customary diluent, diluent or diluent, emulsifier, dispersing and / or binding or fixing agent, wetting agent, water repellent, optionally siccative and UV stabilizers and optionally dyes and pigments, antifoams, Preservatives, secondary thickeners, adhesives, gibberellins and other processing aids.
  • compositions according to the invention comprise not only formulations which are already ready for use and which can be applied to the plant or the seed with a suitable apparatus, but also commercial concentrates which have to be diluted with water before use.
  • the active compounds according to the invention can be used as such or in their (commercially available) formulations and in the formulations prepared from these formulations in admixture with other (known) active ingredients such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides , Fertilizers, safeners or semiochemicals.
  • the treatment according to the invention of the plants and plant parts with the active ingredients or agents is carried out directly or by acting on their environment, habitat or storage space according to the usual treatment methods, e.g. by dipping, (spraying), (spraying), sprinkling, vaporizing, spraying, atomizing, (sprinkling), foaming, brushing, spreading, drenching, drip irrigation and propagating material, especially in seeds by dry pickling, wet pickling, slurry pickling, encrusting, single or multi-layer coating, etc. It is also possible to apply the active ingredients by the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient itself into the soil.
  • the invention further comprises a method of treating seed.
  • the invention further relates to seed which has been treated according to one of the methods described in the previous paragraph.
  • the seeds according to the invention are used in methods for protecting seed from undesirable fungi.
  • a seed treated with at least one active ingredient according to the invention is used.
  • the active compounds or compositions according to the invention are also suitable for the treatment of seed.
  • Much of the crop damage caused by harmful organisms is caused by infestation of the seed during storage or after sowing, and during and after germination of the plant. This phase is particularly critical because the roots and shoots of the growing plant are particularly sensitive and may cause only a small damage to the death of the plant. There is therefore a great interest in protecting the seed and the germinating plant by using suitable means.
  • the present invention therefore also relates to a method of protecting seed and germinating plants from the infestation of phytopathogenic fungi by treating the seed with an agent according to the invention.
  • the invention also relates to the use of the seed treatment agents of the invention for protecting the seed and the germinating plant from phytopathogenic fungi.
  • the invention relates to seed which has been treated with a erf ⁇ ndungswashen agent for protection against phytopathogenic fungi.
  • One of the advantages of the present invention is that due to the particular systemic properties of the active compounds or compositions according to the invention, the treatment of the seeds with these active ingredients or agents protects not only the seed itself, but also the resulting plants after emergence from phytopathogenic fungi , In this way, the immediate treatment of the culture at the time of sowing or shortly afterwards can be omitted.
  • the active compounds or agents according to the invention can also be used in particular in the case of transgenic seed, wherein the plant growing from this seed is capable of expressing a protein which acts against pests.
  • certain pests can already be controlled by the expression of the insecticidal protein, for example.
  • a further synergistic effect can be observed, which additionally increases the effectiveness for protection against pest infestation.
  • compositions according to the invention are suitable for the protection of seed of any plant variety used in agriculture, in the greenhouse, in forests or in horticulture and viticulture.
  • these are seeds of cereals (such as wheat, barley, rye, triticale, millet and oats), maize, cotton, soy, rice, potatoes, sunflower, bean, coffee, turnip (eg. turnip and fodder beet), peanut, oilseed rape, poppy, olive, coconut, cocoa, sugar cane, tobacco, vegetables (such as tomato, cucumber, onions and lettuce), turf and ornamental plants (see also below).
  • cereals such as wheat, barley, rye, triticale and oats
  • maize such as wheat, barley, rye, triticale and oats
  • transgenic seed As also described below, the treatment of transgenic seed with the active compounds or agents according to the invention is of particular importance.
  • This relates to the seed of plants containing at least one heterologous gene which allows expression of a polypeptide or protein having insecticidal properties.
  • the heterologous gene in transgenic seed may e.g. come from microorganisms of the species Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium.
  • this heterologous gene is derived from Bacillus sp., Wherein the gene product has an activity against the European corn borer and / or Western Com Rootworm.
  • the heterologous gene is from Bacillus thuringiensis.
  • the agent according to the invention is applied to the seed alone or in a suitable formulation.
  • the seed is treated in a condition that is so stable that no damage occurs during the treatment.
  • the treatment of the seed can be done at any time between harvesting and sowing.
  • seed is used which has been separated from the plant and freed from flasks, shells, stalks, hull, wool or pulp.
  • seed may be used which has been harvested, cleaned and dried to a moisture content below 15% by weight.
  • seed may also be used which, after drying, e.g. treated with water and then dried again.
  • the agents according to the invention can be applied directly, ie without containing further components and without being diluted. In general, it is preferable to apply the agents to the seed in the form of a suitable formulation. Suitable formulations and methods for seed treatment are known to those skilled in the art and are described, for example, in the following documents: US 4,272,417 A, US 4,245,432 A, US 4,808,430 A, US 5,876,739 A, US 2003/0176428 A1, WO 2002/080675 A1, WO 2002 / 028186 A2.
  • the active compounds which can be used according to the invention can be converted into the customary seed dressing formulations, such as solutions, emulsions, suspensions, powders, foams, slurries or other seed coating compositions, as well as ULV formulations.
  • formulations are prepared in a known manner by mixing the active ingredients with customary additives, such as conventional extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and also Water.
  • customary additives such as conventional extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and also Water.
  • Dyes which may be present in the seed dressing formulations which can be used according to the invention are all dyes customary for such purposes. Both water-insoluble pigments and water-soluble dyes are useful in this case. Examples which may be mentioned under the names rhodamine B, CI. Pigment Red 112 and CI. Solvent Red 1 known dyes.
  • Suitable wetting agents which may be present in the seed dressing formulations which can be used according to the invention are all wetting-promoting substances customary for the formulation of agrochemical active compounds. Preference is given to using alkylnaphthalene sulfonates, such as diisopropyl or diisobutyl naphthalene sulfonates.
  • Suitable dispersants and / or emulsifiers which may be present in the seed dressing formulations which can be used according to the invention are all nonionic, anionic and cationic dispersants customary for the formulation of agrochemical active compounds. Preference is given to using nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants.
  • Particularly suitable nonionic dispersants are, in particular, ethylene oxide-propylene oxide, block polymers, alkylphenol polyglycol ethers and also tristryrylphenol polyglycol ethers and their phosphated or sulfated derivatives.
  • Suitable anionic dispersants are in particular lignosulfonates, polyacrylic acid salts and arylsulfonate-formaldehyde condensates.
  • Defoamers which may be present in the seed-dressing formulations which can be used according to the invention are all foam-inhibiting substances customary for the formulation of agrochemical active compounds.
  • Preferably usable are silicone defoamers and magnesium stearate.
  • Preservatives which may be present in the seed dressing formulations which can be used according to the invention are all substances which can be used for such purposes in agrochemical compositions. Examples include dichlorophen and Benzylalkoholhemiformal. As secondary thickeners which may be present in the seed dressing formulations which can be used according to the invention, all substances which can be used for such purposes in agrochemical compositions are suitable. Preference is given to cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica.
  • Suitable adhesives which may be present in the seed dressing formulations which can be used according to the invention are all customary binders which can be used in pickling agents.
  • Polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and Tylose are preferably mentioned.
  • the gibberellins are known (see R. Wegler "Chemie der convinced- und Swdlingsbekungsstoff", Vol. 2, Springer Verlag, 1970, pp. 401-412).
  • the seed dressing formulations which can be used according to the invention can be used either directly or after prior dilution with water for the treatment of seed of various kinds, including seed of transgenic plants. In this case, additional synergistic effects may occur in interaction with the substances formed by expression.
  • the seed dressing formulations which can be used according to the invention or the preparations prepared therefrom by the addition of water
  • the seed is placed in a mixer which adds either desired amount of seed dressing formulations either as such or after prior dilution with water and mixes until evenly distributed the formulation on the seed.
  • a drying process follows.
  • the active compounds or compositions according to the invention have a strong fungicidal and mycotoxin-reducing action and can be employed for controlling undesirable and mycotoxin-producing fungi in crop protection and in the protection of materials.
  • the 5-pyridin-4yl (1,3-thiazoles) according to the invention can be employed in crop protection for controlling Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
  • the fungicidal compositions according to the invention can be used curatively or protectively for controlling phytopathogenic and mycotoxin-producing fungi.
  • the invention therefore relates also curative and protective methods for controlling phytopathogenic fungi and for reducing mycotoxins in plants and plant parts by the use of the active compounds or agents according to the invention, which are based on the seed, the plant or plant parts, the fruits or the soil in which the plants grow, is applied.
  • the plant or plant material treated with the compounds of formula (I) or (Ia) according to the invention comprises at least 10%, preferably at least 20%, more preferably at least 40% less mycotoxin than a plant or plant material that were not treated.
  • compositions according to the invention for controlling phytopathogenic and mycotoxin-producing fungi in crop protection comprise an effective but non-phytotoxic amount of the active compounds according to the invention.
  • Effective but non-phytotoxic amount means an amount of the agent of the invention sufficient to control or completely kill fungal disease of the plant and at the same time not cause any significant symptoms of phytotoxicity It depends on a number of factors, for example the fungus to be controlled, the plant, the climatic conditions and the ingredients of the agents according to the invention.
  • the good plant tolerance of the active ingredients in the necessary concentrations for controlling plant diseases allows treatment of aboveground plant parts, of plant and seed, and the soil.
  • plants are understood as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
  • Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties which can or can not be protected by plant variety rights.
  • Plant parts are to be understood as meaning all the above-ground and underground parts and organs of the plants, such as shoot, leaf, flower and root, examples of which include leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, and roots, tubers and rhizomes become.
  • the plant parts also include crops and vegetative and generative propagation material, such as seeds, cuttings, tubers, rhizomes, offshoots and seeds.
  • the active compounds according to the invention are suitable for plant compatibility, favorable warm-blood toxicity and good environmental compatibility for the protection of plants and plant organs, for increasing crop yields, improving the quality of the harvested crop. They can preferably be used as crop protection agents. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
  • plants which can be treated according to the invention mention may be made of the following: cotton, flax, grapevine, fruits, vegetables, such as Rosaceae sp. (for example, pome fruits such as apple and pear, but also drupes such as apricots, cherries, almonds and peaches and soft fruits such as strawberries), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp.
  • Rosaceae sp. for example, pome fruits such as apple and pear, but also drupes such as apricots, cherries, almonds and peaches and soft fruits such as strawberries
  • Rosaceae sp. for example, pome fruits such as apple and pear
  • Rubiaceae sp. for example, coffee
  • Theaceae sp. Sterculiceae sp.
  • Rutaceae sp. for example, lemons, organs and grapefruit
  • Solanaceae sp. for example tomatoes
  • Liliaceae sp. Asteraceae sp.
  • Umbelliferae sp. for example, Cruciferae sp., Chenopodiaceae sp.
  • Cucurbitaceae sp. for example cucumber
  • Alliaceae sp. for example leek, Zwie-in
  • Main crops such as Gramineae sp. (for example corn, turf, cereals such as wheat, rye, rice, barley, oats, millet and triticale), Asteraceae sp. (for example sunflower), Brassicaceae sp. (for example, white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes and rapeseed, mustard, horseradish and cress), Fabacae sp. (for example, bean, peanuts), Papilionaceae sp. (for example soybeans), Solanaceae sp. (for example potatoes), Chenopodiaceae sp. (for example, sugar beet, fodder beet, Swiss chard, beet); Useful plants and ornamental plants in the garden and forest; and each genetically modified species of these plants.
  • Gramineae sp. for example corn, turf, cereals such as wheat, rye, rice,
  • plants and their parts can be treated.
  • wild-occurring or by conventional biological breeding methods such as cross-breeding or protoplast fusion obtained plant species and plant varieties and their parts are treated.
  • transgenic plants and plant cultivars obtained by genetic engineering if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated.
  • the term "parts” or “parts of plants” or “parts of plants” has been explained above.Propeas of the respective commercial or in use plant varieties are particularly preferably treated according to the invention. ), which have been bred by either conventional breeding, mutagenesis or recombinant DNA techniques.
  • the treatment method of the invention may be used for the treatment of genetically modified organisms (GMOs), e.g. As plants or seeds are used.
  • GMOs genetically modified organisms
  • Genetically modified plants are plants in which a heterologous gene has been stably integrated into the genome.
  • heterologous gene essentially means a gene which is provided or assembled outside the plant and which, when introduced into the nuclear genome, the chloroplast genome or the hypochondria genome of the transformed plant, imparts new or improved agronomic or other properties to it being of interest Expressing protein or polypeptide or that it is downregulating or shutting down another gene present in the plant or other genes present in the plant (for example by means of antisense technology, cosuppression technology or RNAi technology [RNA Interference]).
  • a heterologous gene present in the genome is also referred to as a transgene.
  • a transgene that is defined by its specific presence in the plant genome is called a transformation or transgenic event.
  • the treatment according to the invention may also lead to over-additive ("synergistic") effects.
  • over-additive additive
  • the following effects are possible, which go beyond the expected effects: reduced application rates and / or extended spectrum of action and / or increased efficacy of the active ingredients and compositions that can be used according to the invention, better plant growth, increased tolerance to high or low Temperatures, increased tolerance to drought or water or soil salinity, increased flowering, harvest relief, ripening, higher yields, larger fruits, greater plant height, intense green color of the leaf, earlier flowering, higher quality and / or higher nutritional value of the harvested products, higher sugar concentration in the fruits, better storage and / or processability of the harvested products.
  • the active compound combinations according to the invention can also exert a strengthening effect on plants. They are therefore suitable for mobilizing the plant defense system against attack by undesirable phytopathogenic fungi and / or microorganisms and / or viruses. This may optionally be one of the reasons for the increased effectiveness of the combinations according to the invention, for example against fungi.
  • Plant-strengthening (resistance-inducing) substances in the present context should also mean those substances or substance combinations which are able to stimulate the plant defense system in such a way that the treated plants, when subsequently inoculated with undesirable phytopathogenic fungi, have a considerable degree of resistance against have these undesirable phytopathogenic fungi.
  • the substances according to the invention can therefore be used for the protection of plants. use attack by the mentioned pathogens within a certain period of time after the treatment. The period of time over which a protective effect is achieved generally extends from 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active substances.
  • Plants and plant varieties which are preferably treated according to the invention include all plants which have genetic material conferring on these plants particularly advantageous, useful features (whether obtained by breeding and / or biotechnology).
  • Plants and plant varieties which are also preferably treated according to the invention are resistant to one or more biotic stressors, i. These plants have an improved defense against animal and microbial pests such as nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and / or viroids.
  • Plants and plant varieties which can also be treated according to the invention are those plants which are resistant to one or more abiotic stress factors.
  • Abiotic stress conditions may include, for example, drought, cold and heat conditions, osmotic stress, waterlogging, increased soil salinity, increased exposure to minerals, ozone conditions, high light conditions, limited availability of nitrogen nutrients, limited availability of phosphorous nutrients, or avoidance of shade.
  • Plants and plant varieties which can also be treated according to the invention are those plants which are characterized by increased yield properties.
  • An increased yield can in these plants z.
  • it may be based on improved plant physiology, improved plant growth and improved plant development, such as water utilization efficiency, water retention efficiency, improved nitrogen utilization, increased carbon assimilation, improved photosynthesis, increased germination power and accelerated maturation.
  • Yield can be further influenced by improved plant architecture (under stress and non-stress conditions), including early flowering, control of flowering for hybrid seed production, seedling growth, plant size, internode count and distance, root growth, seed size, Fruit size, pod size, pod or ear number, number of seeds per pod or ear, seed mass, increased seed filling, reduced seed drop, reduced pod popping and stability.
  • Other yield-related traits include seed composition such as carbohydrate content, protein content, oil content and composition, nutritional value, reduction of nontoxic compounds, improved processability, and improved shelf life.
  • Plants which can be treated according to the invention are hybrid plants which already express the properties of the heterosis or of the hybrid effect, which generally results in higher yields, higher yields and higher yields. herd vigor, better health and better resistance to biotic and abiotic stress factors. Such plants are typically produced by crossing an inbred male sterile parental line (the female crossover partner) with another inbred male fertile parent line (the male crossbred partner). The hybrid seed is typically harvested from the male sterile plants and sold to propagators. Pollen sterile plants can sometimes be produced (eg in maize) by delaving (ie mechanical removal of the male reproductive organs or the male flowers); however, it is more common for male sterility to be due to genetic determinants in the plant genome.
  • a ribonuclease such as a barnase is selectively expressed in the tapetum cells in the stamens.
  • the fertility can then be restorated by expression of a ribonuclease inhibitor such as barstar in the tapetum cells.
  • Plants or plant varieties obtained by methods of plant biotechnology, such as genetic engineering which can be treated according to the invention are herbicide-tolerant plants, i. H. Plants tolerant to one or more given herbicides. Such plants can be obtained either by genetic transformation or by selection of plants containing a mutation conferring such herbicide tolerance.
  • Herbicide-tolerant plants are, for example, glyphosate-tolerant plants, ie plants that have been tolerated to the herbicide glyphosate or its salts.
  • glyphosate-tolerant plants can be obtained by transforming the plant with a gene encoding the enzyme 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS).
  • EPSPS 5-enolpyruvylshikimate-3-phosphate synthase
  • EPSPS 5-enolpyruvylshikimate-3-phosphate synthase
  • EPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonella typhimurium, the CP4 gene of the bacterium Agrobacterium sp., The genes for a EPSPS from the petunia, for a EPSPS from the tomato or for a Encoding EPSPS from Eleusine.
  • Glyphosate-tolerant plants can also be obtained by expressing a gene encoding a glyphosate oxidoreductase enzyme. Glyphosate-tolerant plants can also be obtained by expressing a gene encoding a glyphosate acetyltransferase enzyme. Glyphosate-tolerant plants can also be obtained by selecting plants that naturally select mutations of the genes mentioned above.
  • herbicide-resistant plants are, for example, plants which have been tolerated to herbicides which inhibit the enzyme glutamine synthase, such as bialaphos, phosphinotricin or glufosinate.
  • Such plants can be obtained by expressing an enzyme which detoxifies the herbicide or a mutant of the enzyme glutamine synthase, which is resistant to inhibition.
  • an effective detoxifying enzyme is, for example, an enzyme encoding a phosphinotricin acetyltransferase (such as the bar or pat protein from Streptomyces species). Plants expressing an exogenous phosphinotricin acetyltransferase have been described.
  • hydroxyphenylpyruvate dioxygenase HPPD
  • the hydroxyphenylpyruvate dioxygenases are enzymes that catalyze the reaction in which para-hydroxyphenylpyruvate (HPP) is converted to homogentisate.
  • Plants tolerant of HPPD inhibitors may be transformed with a gene encoding a naturally occurring resistant HPPD enzyme or a gene encoding an imitated HPPD enzyme.
  • Tolerance to HPPD inhibitors can also be achieved by transforming plants with genes encoding certain enzymes that allow the formation of homogentisate despite inhibition of the native HPPD enzyme by the HPPD inhibitor.
  • the tolerance of plants to HPPD inhibitors can also be improved by transforming plants with a gene coding for a prephenate dehydrogenase enzyme in addition to a gene coding for an HPPD tolerant enzyme.
  • ALS inhibitors include sulfonylurea, imidazolinone, triazolopyrimidines, pyrimidinyloxy (thio) benzoates and / or sulfonylaminocarbonyltriazolinone herbicides.
  • ALS also known as acetohydroxy acid synthase, AHAS
  • AHAS acetohydroxy acid synthase
  • plants which are tolerant to imidazolinone and / or sulfonylurea can be obtained by induced mutagenesis, selection in cell cultures in the presence of the herbicide or by mutation breeding.
  • Plants or plant varieties obtained by plant biotechnology methods such as genetic engineering which can also be treated according to the invention are insect-resistant transgenic plants, i. Plants that have been made resistant to attack by certain target insects. Such plants can be obtained by genetic transformation or by selection of plants containing a mutation conferring such insect resistance.
  • insect-resistant transgenic plant includes any plant containing at least one transgene comprising a coding sequence encoding:
  • insecticidal crystal protein from Bacillus thuringiensis or an insecticidal part thereof, such as the insecticidal crystal proteins, available online at:
  • a Bacillus thuringiensis crystal protein or a part thereof which is insecticidal in the presence of a second crystal protein other than Bacillus thuringiensis or a part thereof, such as the binary toxin consisting of the crystal proteins Cy34 and Cy35; or
  • an insecticidal hybrid protein comprising parts of two different insecticidal crystal proteins from Bacillus thuringiensis, such as a hybrid of the proteins of 1) above or a hybrid of the proteins of 2) above, e.g. The protein Cryl A.105 produced by the corn event MON98034 (WO 2007/027777); or
  • a secreted protein from Bacillus thuringiensis or Bacillus cereus which is insecticidal in the presence of a second secreted protein from Bacillus thuringiensis or B. cereus, such as the binary toxin consisting of the proteins VIP 1 A and VCP2A.
  • a hybrid insecticidal protein comprising parts of various secreted proteins of Bacillus thuringiensis or Bacillus cereus, such as a hybrid of the proteins of 1) or a hybrid of the proteins of 2) above; or
  • insect-resistant transgenic plants in the present context also include any plant comprising a combination of genes encoding the proteins of any of the above classes 1 to 8.
  • an insect resistant plant contains more than one transgene encoding a protein of any one of the above 1 to 8 in order to extend the spectrum of the corresponding target insect species or to delay the development of resistance of the insects to the plants by use different proteins which are insecticidal for the same target insect species, but have a different mode of action, such as binding to different receptor binding sites in the insect.
  • Plants or plant varieties obtained by methods of plant biotechnology, such as genetic engineering), which can also be treated according to the invention, are tolerant of abiotic stress factors. Such plants can be through genetic transformation or through Selection of plants containing a mutation conferring such stress resistance. Particularly useful plants with stress tolerance include the following:
  • PARP poly (ADP-ribose) polymerase
  • Plants or plant varieties obtained by plant biotechnology methods, such as genetic engineering which can also be treated according to the invention have a modified amount, quality and / or shelf life of the harvested product and / or altered properties of certain components of the harvested product on, such as:
  • Transgenic plants that synthesize non-starch carbohydrate polymers or non-starch carbohydrate polymers whose properties are altered compared to wild-type plants without genetic modification. Examples are plants that produce polyfructose, particularly of the inulin and levan type, plants that produce alpha-1,4-glucans, plants that produce alpha-1,6-branched alpha-1,4-glucans, and plants that produce Produce alternan.
  • Plants or plant varieties obtained by plant biotechnology methods such as genetic engineering), which can also be treated according to the invention, are plants such as cotton plants with altered fiber properties. Such plants can be obtained by genetic transformation or by selection of plants containing a mutation conferring such altered fiber properties; these include:
  • plants such as cotton plants containing an altered form of cellulose synthase genes
  • plants such as cotton plants, containing an altered form of rsw2 or rsw3 homologous nucleic acids
  • plants such as cotton plants with increased expression of the sucrose phosphate synthase
  • plants such as cotton plants with increased expression of sucrose synthase
  • plants such as cotton plants with modified reactivity fibers, e.g. By expression of the N-acetylglucosamine transferase gene, including nodC, and chitin synthase genes.
  • Plants or plant varieties obtained by plant biotechnology methods such as genetic engineering which can also be treated according to the invention are plants such as oilseed rape or related Brassica plants with altered oil composition properties. Such plants can be obtained by genetic transformation or by selection of plants containing a mutation conferring such altered oil properties; these include:
  • plants such as oilseed rape plants, which produce oil of high oleic acid content
  • plants such as rape plants that produce oil with a low linolenic acid content.
  • transgenic plants such as rape plants that produce oil with a low saturated fatty acid content.
  • Particularly useful transgenic plants which can be treated according to the invention are plants with one or more genes coding for one or more toxins, the transgenic plants offered under the following commercial names: YIELD GARD® (for example maize, cotton, Soybeans), KnockOut® (for example, corn), BiteGard® (for example, corn), BT-Xtra® (for example, corn), StarLink® (for example, corn), Bollgard® (cotton), Nucotn® (cotton) , Nucotn 33B® (cotton), NatureGard® (for example corn), Protecta® and NewLeaf® (potato).
  • YIELD GARD® for example maize, cotton, Soybeans
  • KnockOut® for example, corn
  • BiteGard® for example, corn
  • BT-Xtra® for example, corn
  • StarLink® for example, corn
  • Bollgard® cotton
  • Nucotn®
  • Herbicide-tolerant crops to be mentioned include, for example, corn, cotton and soybean varieties sold under the following tradenames: Roundup Ready® (glyphosate tolerance, for example corn, cotton, soybean), Liberty Link® (phosphinotricin tolerance, for example Rapeseed), IMI® (imidazolinone tolerance) and SCS® (Sylfonylurea tolerance), for example maize.
  • Roundup Ready® glyphosate tolerance, for example corn, cotton, soybean
  • Liberty Link® phosphinotricin tolerance, for example Rapeseed
  • IMI® imidazolinone tolerance
  • SCS® Sylfonylurea tolerance
  • transgenic plants that can be treated according to the invention are plants that contain transformation events, or a combination of transformation events, and that are listed, for example, in the files of various national or regional authorities (see, for example, http: // /gmoinfo.jrc.it/gmp_browse.aspx and http://www.agbios.com/dbase.php).
  • the active compounds or compositions according to the invention can also be used in the protection of materials for the protection of industrial materials against infestation and destruction by undesired microorganisms, such as e.g. Mushrooms, are used.
  • Technical materials as used herein mean non-living materials that have been prepared for use in the art.
  • technical materials to be protected from fungal alteration or destruction by the active compounds of the present invention may be adhesives, glues, paper, wallboard and board, textiles, carpets, leather, wood, paints and plastics, coolants and other materials used by Microorganisms can be attacked or decomposed.
  • the materials to be protected also include parts of production plants and buildings, eg cooling water circuits, cooling and heating systems and ventilation and air conditioning systems, which may be affected by the proliferation of microorganisms.
  • technical materials which may be mentioned are preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer fluids, particularly preferably wood.
  • the active compounds or compositions according to the invention can prevent adverse effects such as decay, deterioration, decomposition, discoloration or mold.
  • Storage Goods are understood natural substances of plant or animal origin or their processing products, which were taken from nature and for long-term protection is desired
  • Storage goods of plant origin such as plants or plant parts, such as stems, leaves, tubers, seeds , Fruits, grains, can be protected in freshly harvested condition or after processing by (pre-) drying, wetting, crushing, grinding, pressing or roasting
  • Storage Goods also includes timber, whether unprocessed, such as timber, power poles and barriers, or in the form of finished products, such as furniture, storage goods of animal origin are, for example, skins, leather, furs and hair.
  • the active compounds according to the invention can prevent disadvantageous effects such as decay, deterioration, disintegration, discoloration or mold.
  • Blumeria species such as Blumeria graminis
  • Podosphaera species such as Podosphaera leucotricha
  • Sphaerotheca species such as Sphaerotheca fuliginea
  • Uncinula species such as Uncinula necator
  • Gymnosporangium species such as Gymnosporangium sabinae
  • Hemileia species such as Hemileia vastatrix
  • Phakopsora species such as Phakopsora pachyrhizi and Phakopsora meibomiae
  • Puccinia species such as Puccinia recondita or Puccinia triticina
  • Uromyces species such as Uromyces appendiculatus
  • Bremia species such as Bremia lactucae
  • Peronospora species such as Peronospora pisi or P. brassicae
  • Phytophthora species such as Phytophthora infestans
  • Plasmopara species such as Plasmopara viticola
  • Pseudoperonospora species such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis
  • Pythium species such as Pythium ultimum
  • Leaf spot diseases and leaf wilt caused by, for example, Alternaria species such as Alternaria solani; Cercospora species, such as Cercospora beticola; Cladiosporum- Species such as Cladiosporium cucumerinum; Cochliobolus species, such as Cochliobolus sativus (conidia form: Drechslera, Syn: Helminthosporium); Colletotrichum species, such as Colletotrichum lindemuthanium; Cycloconium species, such as, for example, cycloconium oleaginum; Diaporthe species, such as Diaporthe citri; Elsinoe species, such as Elsinoe fawcettii; Gloeosporium species, such as, for example, Gloeosporium laeticolor; Glomerella species, such as Glomerella cingulata; Guignardia species, such as Guignardia bidwelli; Leptosphaeria species
  • Phaeosphaeria species such as Phaeosphaeria nodorum
  • Pyrenophora species such as, for example, Pyrenophora teres
  • Ramularia species such as Ramularia collo-cygni
  • Rhynchosporium species such as Rhynchosporium secalis
  • Septoria species such as Septoria apii
  • Typhula species such as Typhula incarnata
  • Venturia species such as Venturia inaequalis
  • Root and stem diseases caused by e.g. Corticium species such as, for example, Cor- ticium graminearum; Fusarium species such as Fusarium oxysporum; Gaeumannomyces species such as Gaeumannomyces graminis; Rhizoctonia species, such as Rhizoctonia solani; Tapesia species, such as Tapesia acuformis; Thielaviopsis species, such as Thielaviopsis basicola;
  • Ear and panicle diseases caused by e.g. Alternaria species, such as Alternaria spp .; Aspergillus species, such as Aspergillus flavus; Celadporium species such as, for example, Cladosporium cladosporioides; Claviceps species, such as Claviceps purpurea; Fusarium species such as Fusarium culmorum; Gibberella species, such as Gibberella zeae; Monographella species, such as Monographella nivalis; Septoria species such as Septoria nodorum;
  • Sphacelotheca species such as Sphacelotheca reiliana
  • Tilletia species such as Tilletia caries, T. controversa
  • Urocystis species such as Urocystis occulta
  • Ustilago species such as Ustilago nuda, U. nuda tritici
  • Nectria species such as Nectria galligena
  • Deformations of leaves, flowers and fruits caused by e.g. Taphrina species such as, for example, Taphrina deformans;
  • Botrytis species such as Botrytis cinerea
  • Rhizoctonia species such as Rhizoctonia solani
  • Hehninthosporium species such as Helminthosporium solani
  • Xanthomonas species such as Xanthomonas campestris pv. Oryzae
  • Pseudomonas species such as Pseudomonas syringae pv. Lachrymans
  • Erwinia species such as Erwinia amylovora
  • the following diseases of soybean beans can be controlled:
  • Fungus diseases on leaves, stems, pods and seeds caused by, for example, Alternaria leaf spot (Alternaria spec. Atrans tenuissima), Anthracnose (Colletotrichum gloeosporoides dematium var.
  • Phytophthora red (Phytophthora megasperma), Brown Stem Red (Phialophora gregata), Pythium Red (Pythium aphanidermatum, Pythium irregular, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), Rhizoctonia Root Red, Stem Decay, and Damping Off (Rhizoctonia solani), Sclerotinia Stem Decay (Sclerotinia sclerotiorum), Sclerotinia Southern Blight (Sclerotinia rolfsii) , Thielaviopsis Root Red (Thielaviopsis basicola).
  • the active compounds according to the invention preferably act against fungi, in particular molds, wood-discolouring and wood-destroying fungi (Basidiomycetes).
  • fungi in particular molds, wood-discolouring and wood-destroying fungi (Basidiomycetes).
  • Basidiomycetes fungi of the following genera: Alternaria, such as Alternaria tenuis; Aspergillus, such as Aspergillus niger; Chaetomium, like Chaetomium globosum; Coniophora, such as Coniophora pentana; Lentinus, like 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.
  • the application rates can be varied within a relatively wide range, depending on the mode of administration.
  • the application rate of the active compounds according to the invention is
  • Leaves from 0.1 to 10,000 g / ha, preferably from 10 to 1,000 g / ha, more preferably from 50 to 300 g / ha (when used by pouring or drop, the application rate can even be reduced, especially if inert substrates such as rockwool or perlite are used);
  • seed treatment from 2 to 200 g per 100 kg of seed, preferably from 3 to 150 g per 100 kg of seed, more preferably from 2.5 to 25 g per 100 kg of seed, most preferably from 2.5 to 12, 5 g per 100 kg of seed;
  • the active compounds or compositions according to the invention can therefore be used to protect plants within a certain period of time after the treatment against attack by the mentioned pathogens.
  • the period within which protection is brought about generally lasts from 1 to 28 days, preferably from 1 to 14 days, particularly preferably from 1 to 10 days, very particularly preferably from 1 to 7 days after the treatment of the plants the active substances or up to 200 days after seed treatment.
  • Deoxynivalenol (DON), Nivalenol, 15-Ac-DON, 3-Ac-DON, 4-Acetylnalenol (Fusarenon-X), 4,15-Diacetylnivalenol, 4, are particularly, but not exclusively, mentioned here.
  • the plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula (I) the agents according to the invention.
  • the preferred ranges given above for the active compounds or agents also apply to the treatment of these plants. Particularly emphasized is the plant treatment with the compounds or agents specifically mentioned in the present text.
  • the calibration is carried out with unbranched alkan-2-ones (with 3 to 16 carbon atoms), whose logP values are known (determination of the logP values by means of the retention times by linear interpolation between two consecutive alkanones).
  • the lambda-maX values were determined on the basis of the UV spectra from 200 nm to 400 nm in the maxima of the chromatographic signals.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • inventive compound examples Nos. 2, 3, 5, 6, 9, 12, 14, 16, 17, 21, 22, 24, 26, 32, 33, 35, 36, 37, 38, 39, 40 show , 41, 42, 47, 51, 58, 71, 72, 74, 76, 79 and 104 of Tables 1 and 2 at an active ingredient concentration of 500ppm have an efficiency of 70% or more.
  • the compounds were grown in microtiter plates at 5 concentrations of 0.08 ⁇ M to 50 ⁇ M in a fumonisin-inducing liquid medium (0.5 g malt extract, Ig yeast extract, Ig Bactopeptone, 20 g fructose, Ig KH 2 PO 4 , 0.3 g MgSO 4 .7H 2 O, 0.3g KCl, 0.05g ZnSO 4 x 7H 2 O, and 0.01g CuSO 4 x 5H 2 O per liter) with DMSO (0.5%).
  • the inoculation was carried out with a concentrated spore suspension of Fusarium proliferatum at a final concentration of 2000 spores / ml.
  • the plate was incubated at high humidity for 5 days at 20 0 C.
  • Example 3 Production of DON / acetyl-DON by Fusarium graminearum
  • the compounds were grown in microtiter plates at 7 concentrations from 0.07 ⁇ M to 50 ⁇ M in a DON-inducing liquid medium (Ig (NH 2 ) 2 HPO 4 , 0.2 g MgSO 4 .7H 2 O, 3 g KH 2 PO 4 , 10 g glycerol , 5g NaCl and 40g sucrose per liter) with oat extract (10%) and DMSO (0.5%).
  • the inoculation was carried out with a concentrated spore suspension of Fusarium graminearum at a final concentration of 2000 spores / ml.
  • the plate was incubated at high humidity for 7 days at 28 0 C.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Emulsifier 1 part by weight of alkyl-aryl-polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • inventive compound examples Nos. 3, 6, 16, 17, 19, 21, 24, 26, 27, 28, 30, 31, 32, 33, 35, 36, 37, 41, 42, 43, 44 show , 45, 48, 51, 53, 56, 57, 76, 78, 79 and 103 of Tables 1 and 2 at an active ingredient concentration of 500ppm have an efficiency of 70% or more.
  • Example 8 Septoria tritici test (wheat) / protective
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Example 10 Fumonisin FBI production by Fusarium verticillioides
  • Fumonisin-inducing liquid medium (Jimenez et al. (2003) Int. J. Food Microbiol. 89, 185-193) was ver ⁇ cz with a concentrated Fusarium / Vz 'o ⁇ fey spore suspension of 350,000 spores / ml (at -160 0 C stored) inoculated. This gave a final concentration of 2,000 spores / ml in the so-called inoculation medium.
  • the example compounds were prepared as a 10 mM stock solution in 100% DMSO and diluted to 1 UiM in H 2 O. The substances were tested in a final concentration of 50 ⁇ M.
  • a sample of the liquid medium was removed and diluted in 10% acetonitrile (v / v).
  • the samples were appropriately diluted in acetonitrile to determine the fumonisin FBI concentrations by HPLC-MS / MS.
  • the results were used to calculate the percentage inhibition of mycotoxin biosynthesis.
  • 0% means an efficiency which corresponds to the fumonisin FBl content of the positive control
  • an efficiency of 100% means that the fumonisin FB1 concentration of the sample after dilution was below the analytical detection threshold of 0.1 ng / ml.
  • the dynamic difference between the positive control and the sample detection limit is at least a factor of 200.
  • Examples Nos. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 and 11 of Table I show efficiencies of 70% or greater at 50 ⁇ M active ingredient concentration.
  • Example 11 DON / acetyl-DON production by Fusarium ⁇ raminearum
  • DON-inducing liquid medium production medium - modified myro
  • H 2 O dissolved oat extract
  • a concentrated Fusarium graminearum spore suspension of 200,000 spores / ml (at -160 0 C stored) 10% inoculated (w / v). This gave a final concentration of 2,000 spores / ml in the so-called inoculation medium
  • Substances were prepared as 10 mM stock solution in 100% DMSO and diluted to 1 mM in H 2 O. The substances were tested in a final concentration of 50 ⁇ M.
  • 0% means an efficiency which corresponds to that of the positive control
  • an efficiency of 100% means that the mycotoxin concentration of the sample after dilution was below the analytical detection threshold of 0.1 ng / ml.
  • the dynamic difference between the positive control and the sample detection limit is at least a factor of 200. Both Don and Ac-Don were measured. Both mycotoxin values were added together for evaluation and considered together.
  • Examples Nos. 3 and 5 of Table I show efficiencies of 70% or greater at 50 ⁇ M active ingredient concentration.

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

Abstract

La présente invention concerne l'utilisation de 5-pyridine-4-yl(1,3)thiazoles connus pour la lutte contre les champignons phytopathogènes dans des plantes ou parties de plantes, ainsi qu'un procédé de lutte contre les champignons phytopathogènes dans des plantes ou parties de plantes dans le domaine de la protection des plantes, ainsi qu'un agent de protection des plantes contenant ces 5-pyridine-4-yl(1,3)thiazoles.
EP09764746A 2008-12-19 2009-12-08 Utilisation de 5-pyridine-4-yl(1,3)thiazoles pour la lutte contre les champignons phytopathogènes Withdrawn EP2378880A1 (fr)

Priority Applications (1)

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EP09764746A EP2378880A1 (fr) 2008-12-19 2009-12-08 Utilisation de 5-pyridine-4-yl(1,3)thiazoles pour la lutte contre les champignons phytopathogènes

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EP08172228A EP2198710A1 (fr) 2008-12-19 2008-12-19 Utilisation de 5-pyridine-4yl-(1,3)thiazoles destinés à lutter contre les champignons phytopathogènes
PCT/EP2009/008737 WO2010069494A1 (fr) 2008-12-19 2009-12-08 Utilisation de 5-pyridine-4-yl(1,3)thiazoles pour la lutte contre les champignons phytopathogènes
EP09764746A EP2378880A1 (fr) 2008-12-19 2009-12-08 Utilisation de 5-pyridine-4-yl(1,3)thiazoles pour la lutte contre les champignons phytopathogènes

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EP2378880A1 true EP2378880A1 (fr) 2011-10-26

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EP09764746A Withdrawn EP2378880A1 (fr) 2008-12-19 2009-12-08 Utilisation de 5-pyridine-4-yl(1,3)thiazoles pour la lutte contre les champignons phytopathogènes

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EA (1) EA201170849A1 (fr)
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Also Published As

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CA2747303A1 (fr) 2010-06-24
BRPI0923197A2 (pt) 2016-06-07
EP2198710A1 (fr) 2010-06-23
US9198426B2 (en) 2015-12-01
WO2010069494A8 (fr) 2011-05-05
MX2011006144A (es) 2011-06-27
WO2010069494A1 (fr) 2010-06-24
US20100168185A1 (en) 2010-07-01
EA201170849A1 (ru) 2012-02-28

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