EP2486031A2 - Phenylpyri(mi)dinylpyrazoles et leur utilisation comme fongicides - Google Patents

Phenylpyri(mi)dinylpyrazoles et leur utilisation comme fongicides

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Publication number
EP2486031A2
EP2486031A2 EP10767974A EP10767974A EP2486031A2 EP 2486031 A2 EP2486031 A2 EP 2486031A2 EP 10767974 A EP10767974 A EP 10767974A EP 10767974 A EP10767974 A EP 10767974A EP 2486031 A2 EP2486031 A2 EP 2486031A2
Authority
EP
European Patent Office
Prior art keywords
alkyl
cycloalkyl
cyano
compounds
ethyl
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Withdrawn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
EP10767974A
Other languages
German (de)
English (en)
Inventor
Alexander Sudau
Mazen Es-Sayed
Christoph Andreas Braun
Ruth Meissner
Catherine Sirven
Jürgen BENTING
Peter Dahmen
Daniela Portz
Ulrike Wachendorff-Neumann
Philippe Desbordes
Samir Bennabi
Christophe Catherin
Anne-Sophie Rebstock
Marie-Claire Grosjean-Cournoyer
Hiroyuki Hadano
Thomas Knobloch
Philippe Rinolfi
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
Original Assignee
Bayer Cropscience AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer Cropscience AG filed Critical Bayer Cropscience AG
Priority to EP14172040.9A priority Critical patent/EP2784070A1/fr
Priority to EP10767974A priority patent/EP2486031A2/fr
Priority to EP14172041.7A priority patent/EP2784071A1/fr
Priority to EP14172042.5A priority patent/EP2784072A1/fr
Priority to EP14172043.3A priority patent/EP2784073A1/fr
Publication of EP2486031A2 publication Critical patent/EP2486031A2/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Withdrawn legal-status Critical Current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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • A01N43/84—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 six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
    • A61K31/41—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having five-membered rings with two or more ring hetero atoms, at least one of which being nitrogen, e.g. tetrazole
    • A61K31/415—1,2-Diazoles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
    • A61K31/435—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with one nitrogen as the only ring hetero atom
    • A61K31/44—Non condensed pyridines; Hydrogenated derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
    • A61K31/495—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with two or more nitrogen atoms as the only ring heteroatoms, e.g. piperazine or tetrazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/22—Tin compounds
    • C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen

Definitions

  • the present invention relates to novel phenylpyri (mi) dinylazoles, several processes for their preparation and their use for controlling unwanted microorganisms in crop protection and material protection and for the reduction of mycotoxins in plants and parts of plants.
  • the present invention further relates to a method for controlling phytopathogenic fungi and for the reduction of mycotoxins in plants and parts of plants in crop protection and crop protection compositions containing phenylpyri (mi) dinylazoles.
  • WO 98/052937 describes certain heteroaryl-substituted pyrazoles which can be used medicinally, in this case for the inhibition of the production of inflammatory cytokines and for the treatment of human p38 kinase-mediated diseases. Similar compounds are also described in EP-A-1 553 096, WO 04/029043, WO 98/052940, WO 00/031063, WO 95/031451, WO 02/057265 and WO 00/039116. However, an effect on fungal pathogens is not described.
  • WO 07/105058 describes certain heteroaryl-substituted pyrazoles which can be used as modulators or inhibitors of the human Raf enzyme. However, the effect on fungal pathogens is not described.
  • X 1 is CH or N
  • R 1 is in each case optionally mono- or polysubstituted by identical or different substituents R 7 -substituted phenyl, naphthalenyl, quinolin-5-yl, quinolin-8-yl, isoquinolin-5-yl, isoquinolin-8-y 1, 1 -benzothiophene-4 -yl, 1-benzothiophene-7-yl, 1-benzofuran-4-yl, 1-benzofuran-7-yl, 1,3-benzodioxol-4-yl or 1,3-benzodioxol-5-yl,
  • R2 is cyano, nitro, halogen, Ci-C 6 alkyl, Ci-C 6 alkoxy, Ci-C 6 haloalkyl, Ci-C 6 -
  • Haloalkoxy Ci-Ce-alkylthio, Cs-Ce-cycloalkyl, C3-C6-halocycloalkyl, C2-C9-heterocyclyl or hydrogen,
  • R 3 is in each case optionally mono- or polysubstituted by identical or different
  • R 4 is hydrogen, halogen, cyano, -C (O) OR 12 , -SR 12 , -NR 12 R 13 , -C (O) NR 12 R 13 or
  • R 5 and R 6 independently of one another represent hydrogen, fluorine, chlorine, bromine, cyano,
  • R 11 is substituted C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 - alkynyl, C 6 -C 4 aryl, - 0- (Ci-C4 alkyl), -0- (C 6 -C 4 aryl), -S- (C r C 4 alkyl), -S ( 0) - (Ci-C 6 alkyl) or -C (0) - (Ci-Ce-alkyl), or together with the carbon atom to which they are attached, one optionally single or multiple, same or different Halogen, oxygen, cyano or C 1 -C 4 -alkyl-substituted cycle (preferably a saturated, unsaturated or partially unsaturated monocycle) with 3,
  • R 7 independently of one another represents one or more of the following groups: fluorine, chlorine,
  • R 11 is -OH, fluorine, chlorine, bromine, cyano, -NH-C (O) R 20 , -NR 20 R 21 , -C (O) R 20 , -C (O) OR 20 ,
  • -C (O) NR 20 R 21 , -SO 2 R 20 or in each case optionally mono- or polysubstituted or differently by fluorine, chlorine, bromine, -OH, carbonyl, cyano, C 1 -C 6 -alkyl or -O- ( C 1 -C 4 -alkyl) substituted Cr Cs-alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C u heteroalkyl, C 3 -C 8 cycloalkyl, -0- (C r C 4 - alkyl), -S- (C r C 4 alkyl), -0- (C 3 -C 8 cycloalkyl), -S- (C 3 -C 8 cycloalkyl), C 6 -C 4 aryl, -O- (C 6 - Ci 4 -aryl), -S- (C 6 -C 4 -aryl), C 2 -C 9
  • R and R independently of one another are C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl or hydrogen, and also agrochemically active salts thereof.
  • X 1 stands for N
  • R 1 is an optionally substituted phenyl
  • R 3 is butyl or propyn-2-yl
  • R 4 stands for NHR 12
  • R 12 is optionally substituted C 6 -C 14 aryl
  • R 2 , R 4 , R 5 , R 6 are H
  • R 3 is methyl, ethyl, allyl, 2-methoxyethyl or benzyl when R 1 is 4-chlorophenyl, or
  • R 3 is methyl when R 1 is phenyl, 4-methoxyphenyl or 4-fluorophenyl.
  • the phenylpyri (mi) -dinylazoles of the invention are generally defined by the formula [Ia].
  • Preferred radical definitions of the above and below formulas are as follows specified. These definitions apply equally to the end products of formula [Ia] as well as to all intermediates.
  • Preferred compounds of the formula [I-a] of the present invention are those in which one or more of the symbols have one of the following meanings:
  • X 1 is CH or N
  • R 1 represents in each case optionally mono- or polysubstituted by identical or different substituents R 7 substituted phenyl, naphthalenyl, quinoline-5-yl, quinolin-8-yl, isoquinolin-5-yl, isoquinolin-8-yl, l, 3-benzodioxole 4-yl or 1,3-benzodioxol-5-yl,
  • R 2 is cyano, nitro, halogen, Ci-C 6 alkyl, Ci-C 6 alkoxy, Ci-C 6 haloalkyl, Ci-C 6 -
  • Haloalkoxy C 1 -C 6 -alkylthio, C 3 -C 6 -cycloalkyl, C 3 -C 6 -halocycloalkyl, C 2 -C 9 -heterocyclyl or hydrogen,
  • R 3 is in each case optionally mono- or polysubstituted by identical or different
  • R 4 is hydrogen, -NR 12 R 13 , -C (O) NR 12 R 13 , wherein R 4 is preferably hydrogen or NHR 13 , wherein then R 13 is in each case optionally mono- or polysubstituted or differently by fluorine, chlorine , bromine, - OH or cyano substituted Ci-C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 - alkynyl, Cs-Cg-cycloalkyl, C2-C9 heterocyclyl or C2-C9 heteroaryl,
  • R 5 and R 6 independently of one another represent hydrogen, fluorine, chlorine, bromine, cyano, nitro, -OH, -SH, or the same for each case optionally mono- or polysubstituted or different substituents R 11 substituted C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -0- (C r C 4 - alkyl), -S- (C r C 4 alkyl) or -S (0) - (C r C 6 alkyl), or furthermore together with the carbon atoms to which they are attached, an optionally mono- or polysubstituted, identically or differently, by halogen, oxygen, cyano or C 1 -C 4 -alkyl-substituted, saturated, unsaturated or partially unsaturated monocycle having 3 to 8 ring atoms, where the monocycle contains heteroatoms from the series consisting of oxygen, sulfur or
  • R and / or R is -C (O) NR R, together with the nitrogen atom to which they are attached form a 3 to 7-membered ring which contains a further nitrogen atom not directly adjacent to the nitrogen from the series N, O may contain R iy is H, C r C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 -alkynyl, -C (S) R, -
  • R 20 and R 21 independently of one another are each optionally mono- or polysubstituted by identical or different substituents by fluorine, chlorine, bromine, -OH or cyano-substituted C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl , C 2 -C 6 -alkynyl or for hydrogen,
  • R 22 and R 23 independently of one another are C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl or hydrogen, and also agrochemically active salts thereof.
  • X 1 stands for CH
  • R 1 is in each case optionally mono- or polysubstituted by identical or different substituents R 7 -substituted phenyl or naphthalenyl,
  • R 2 is halogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl or hydrogen,
  • R 3 is propan-2-yl, isobutyl, butan-2-yl, 2-methylpropyl, 2,2-dimethylpropyl, 3
  • R 15 and R 16 are each independently of the other optionally C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl which is optionally monosubstituted or polysubstituted by identical or differently and R 11 is
  • R 19 is H, C 2 -C 6 -alkynyl, C (O) R 15 , SO 2 R 15 , C (O) OR 15 ,
  • R 20 and R 21 independently of one another are each optionally mono- or polysubstituted identically or differently by C 1 -C 6 -alkyl substituted by fluorine, chlorine, bromine, -OH, cyano, C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C C 2 -C 6 alkynyl or for hydrogen, as well as agrochemically active salts thereof.
  • X 1 is CH
  • R 1 is optionally mono- or polysubstituted by identical or different substituents R 7 -substituted phenyl,
  • R 2 is methyl, ethyl, isopropyl, cyclopropyl or hydrogen
  • R 3 is propan-2-yl, isobutyl, butan-2-yl, 2-methylpropyl, 2,2-dimethylpropyl, 3
  • Methyl, ethyl, 1-propyl or 2-chloroethyl, in a preferred variant R 3 is as defined above but does not include methyl or ethyl.
  • R 4 is hydrogen, -NR 12 R 13 or -NHR 13 , where R 4 is preferably hydrogen,
  • R 7 independently of one another represents one or more of the following groups: fluorine, chlorine,
  • R 11 is -OH, fluorine, chlorine, bromine, cyano, -NH-C (O) R 20 , -C (O) R 20 , -C (O) OR 20 , -
  • R 12 is -C (S) R 15 , -C (O) R 15 , -SO 2 R 15 , -C (O) OR 15 , -OR 15 or -C (O) NR 15 R 16 ,
  • R 13 is C r C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 2 -C 9 heterocyclyl, or C 2 -C 9 -
  • R 15 is in each case optionally mono- or polysubstituted by identical or different
  • Ci-C6-alkyl substituted Ci-C6-alkyl, C3-C6-cycloalkyl, C 2 - C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 2 C 9 heterocyclyl, C 2 C 9 heteroaryl or hydrogen
  • R 16 is hydrogen, methyl, ethyl or propyl
  • R 19 is H, C 2 -C 6 -alkynyl, -C (O) R 15 , -SO 2 R 15 , -C (O) OR 15 ,
  • R 20 and R 21 independently of one another are each optionally mono- or polysubstituted identically or differently by fluorine, chlorine, bromine, OH, cyano-substituted methyl, ethyl, propyl, isopropyl, cyclopropyl, cyclobutyl or for hydrogen, and also agrochemically active salts thereof ,
  • X 1 stands for CH
  • R 1 is phenyl, 3-methylphenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 3
  • R 2 is methyl, ethyl, isopropyl, cyclopropyl, or hydrogen,
  • R 3 is propan-2-yl, isobutyl, butan-2-yl, 2-methylpropyl, 2,2-dimethylpropyl, prop-2-yl-1, but-3-yn-2-yl, C cyclopentyl, cyclopentyl, (2,2-dichlorocyclopropyl) methyl, cyclopropylmethyl, 1-cyclopropylethyl, trifluoromethyl, trichloromethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, 2-chloroethyl, 2-fluoropropyl, 3-fluoropropyl, 1,3-difluoropropan-2-yl, 2-fluorobenzyl, 2,3-
  • R 11 is -OH, fluorine, chlorine, cyano, C r C 6 alkyl, C 2 -C 6 alkenyl or C 2 -C 6 alkynyl, C 3 -C 6 -
  • R 19 is H, acetyl, ethoxycarbonyl, methoxycarbonyl, prop-2-yn-1-yl or but-2-yn-1-yl, and agrochemically active salts thereof.
  • R 4 is H
  • R 3 is propan-2-yl, isobutyl, butan-2-yl, 2-methylpropyl, prop-2-yn-1-yl, cyclopropyl,
  • R 1 is in each case optionally mono- or polysubstituted by identical or different substituents R 7 -substituted phenyl or naphthalenyl,
  • R 2 is halogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl or hydrogen, R 3 is in each case optionally mono- or polysubstituted by identical or different
  • Ci-C6 alkyl is hydrogen, -C (O) NR 12 R 13 or -NR 12 R 13 , wherein R 4 is preferably -NHR 13 , and R 13 is in each case optionally mono- or polysubstituted or differently by fluorine, chlorine , Bromine, -OH, cyano substituted Cp C 6 alkyl, C 3 -C 6
  • R 12 and R 13 independently of one another represent one or more of the following groups: H, -C (S) R 15 ,
  • -C (O) R 15 -SO 2 R 15 , -C (O) OR 15 , -OR 15 or -C (O) NR 15 R 16 or for each optionally mono- or polysubstituted or differently by fluorine, chlorine, bromo, -OH, cyano substituted C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -
  • R 15 and R 16 independently of one another are each optionally mono- or polysubstituted by identical or different substituents
  • R 11 is substituted C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -Cg -cycloalkyl, C 2 -C 9 -heterocyclyl, C 2 -C 9 -heteroaryl or for hydrogen or together with the nitrogen atom to which they are attached form a 3- to 7-membered ring which forms another heteroatom not adjacent to the nitrogen may contain N, O,
  • R 19 is H, C 2 -C 6 alkynyl, -C (O) R 15 , -S0 2 R 15 , -C (O) OR 15 , R 20 and R 21 independently of one another are each optionally mono- or polysubstituted identical or different manner by fluorine, chlorine, bromine, -OH, cyano substituted Ci-C6-alkyl, C3 -C6- cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, or hydrogen, and agrochemically active Salts thereof.
  • N is N, represents optionally mono- or polysubstituted by identical or different substituents R 7 substituted phenyl, represents methyl, ethyl, isopropyl, cyclopropyl or hydrogen, is methyl, ethyl, 1-propyl, propan-2-yl, isobutyl, butan-2-yl , 2-methylpropyl, 2,2-dimethylpropyl, 3-methylbut-2-en-1-yl, but-2-en-1-yl, but-3-en-2-yl, propadienyl, prop-2-yn -l -yl, B ut-2-yn-1-yl, but-3-yn-2-yl, 2-methylbut-3-yn-2-yl, 2-methylbut-3-yn-2-yl, Cyanomethyl, 2-cyanoethyl, 1-cyan
  • R is -OH, fluorine, chlorine, bromine, cyano, -NH-C (0) R 20, -C (0) R 20, -C (0) OR 20, - C (O) NR 20 R 21, -S0 2 R 20 or by identical or different fluorine, chlorine, bromine, OH, cyano, C r C in each case optionally mono- or polysubstituted 6 alkyl or -0- (C r C 4 alkyl) substituted C r C 6 - alkyl, C 3 -C 8 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -0- (C r C 4 alkyl), -S- (C r C 4 alkyl), -O- (C 3 -C 8 -cycloalkyl) or -S- (C 3 -C 8 -cycloalkyl),
  • R is -C (S) R 15 , -C (O) R 15 , -SO 2 R 15 , -C (O) OR 15 , -OR 15 or -C (O) NR 15 R 16 , R is C r C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl C 2 -C 9 heterocyclyl, or C 2 -C 9 - heteroaryl, or hydrogen,
  • R is in each case optionally mono- or polysubstituted by identical or different
  • R is hydrogen, methyl, ethyl or propyl
  • R is H, C 2 -C 6 -alkynyl, -C (O) R 15 , -SO 2 R 15 , -C (O) OR 15 , each independently of one another are optionally mono- or polysubstituted or differently by fluorine, Chlorine, bromine, -OH, cyano substituted methyl, ethyl,
  • R is phenyl, 4-fluorophenyl
  • R 19 is H, acetyl, ethoxycarbonyl, methoxycarbonyl, prop-2-yn-1-yl or but-2-yn-1-yl, as well as agrochemically active salts thereof.
  • Very particularly preferred compounds of the formula [I-a] of the first and second embodiments of the present invention are those in which one or more of the symbols have one of the following meanings:
  • R 1 very particularly preferably represents 4-fluorophenyl, 3-chlorophenyl, 2,6-difluorophenyl, or 3-methylphenyl and in particular 4-fluorophenyl,
  • R 2 very particularly preferably represents cyclopropyl, ethyl, methyl or hydrogen and in particular hydrogen, R 5 and R 6 are very particularly preferably both hydrogen.
  • Preferred areas can be combined as desired. They apply accordingly to the end products as well as to the precursors and intermediates. In addition, individual definitions can be omitted. Preference is given to those compounds of the formula [I-a] in which all radicals each have the abovementioned preferred meanings.
  • X 1 is CH or N
  • R 1 represents in each case optionally mono- or polysubstituted by identical or different substituents R 7 substituted phenyl, naphthalenyl, quinoline-5-yl, quinolin-8-yl, isoquinolin-5-yl,
  • R 2 is cyano, nitro, halogen, Ci-C 6 alkyl, Ci-C 6 alkoxy, Ci-C 6 haloalkyl, Ci-C 6 -
  • Haloalkoxy C 1 -C 6 -alkylthio, C 1 -C 6 -cycloalkyl, C 3 -C 6 -halocycloalkyl, C 2 -C 9 -heterocyclyl or hydrogen,
  • R 301 stands for -C (O) N (R 9 R 10 ), -C (O) R 9 , -C (O) OR 9 , -S (O) 2 R 9 or, if appropriate, in each case monosubstituted or polysubstituted, or different substituents R 8 substituted C Coe -alkyl, C 2 -C6- alkenyl, C 3 -C 6 allenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C r C 6 alkoxy, C 2 -C 9 -, R 401 heterocyclyl, C2 -C9-OxoHeterocyclyl, or heteroaryl, (-CcrHeteroaryl preferably C 2) is -NR 12 R 13, -C (0) NR 12 R 13 or (-N R 12 ) 2
  • R 5 and R 6 independently of one another are hydrogen, fluorine, chlorine, bromine, cyano, nitro, -OH, -SH, or for each optionally mono- or polysubstituted by identical or different substituents R 11 -substituted C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 6 -C 4 -aryl, - 0- (Ci-C4 alkyl), -0- (C 6 -C 4 aryl), -S- (C r C 4 alkyl), -S (0) - (C r C 6 alkyl) or -C (O) - (Ci-Ce-alkyl), or together with the carbon atoms to which they are attached, also form one optionally mono- or polysubstituted by identical or different halogen, oxygen, cyano or Ci-C
  • R 12 is -C (S) R 15 , -C (O) R 15 , -SO 2 R 15 , -C (O) OR 15 , -OR 15 or -C (O) NR 15 R 16 , R 13 is optionally in each case optionally mono- or polysubstituted or differently by fluorine,
  • R 19 is H, C r C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 -alkynyl, -C (S) R 15, -
  • R 20 and R 21 are independently of one another in each case optionally monosubstituted or polysubstituted by identical or different substituents C 1 -C 6 -alkyl substituted by fluorine, chlorine, bromine, -OH or cyano
  • Cycloalkyl C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or hydrogen, and agrochemically active salts thereof.
  • inventive phenylpyri (mi) dinylazoles of the formula [I-b] have very good microbicidal properties and can be used for the protection of materials and for the reduction of mycotoxins in plants and parts of plants.
  • the phenylpyri (mi) -dinylazoles of the invention are generally defined by the formula [I-b].
  • Preferred radical definitions of the above and below formulas are given below. These definitions apply equally to the end products of the formula [I-b] as well as to all intermediates.
  • X 1 is CH or N
  • R 1 represents in each case optionally mono- or polysubstituted by identical or different substituents R 7 substituted phenyl, naphthalenyl, quinoline-5-yl, quinolin-8-yl, isoquinolin-5-yl, isoquinolin-8-yl, l, 3-benzodioxole 4-yl or 1,3-benzodioxol-5-yl,
  • R 2 represents cyano, halogen, Ci-C 6 alkyl, Ci-C 6 alkoxy, Ci-C 6 haloalkyl, C r C 6 -
  • Haloalkoxy C 1 -C 6 -alkylthio, C 3 -C 6 -cycloalkyl, C 3 -C 6 -halocycloalkyl, C 2 -C 9 -heterocyclyl or hydrogen,
  • R 301 stands for -C (O) R 9 , -C (O) OR 9 , -S (O) 2 R 9 or C 1 -C 6 -alkyl, C 2, which is optionally monosubstituted or polysubstituted by identical or different substituents by R 8 -C 6 alkenyl, C 3 .6-allenyl, C 2 -6-alkynyl, C 3 -C 8 cycloalkyl, C r C6-alkoxy, C2 -C9 heterocyclyl, C2 -C9-Oxoheterocyclyl, or heteroaryl , R 4 4 0 U 1 1 stands for -NR 12 R 13,
  • R 5 and R 6 independently of one another represent hydrogen, fluorine, chlorine, bromine, cyano, nitro, -OH, -SH, or in each case optionally mono- or polysubstituted by identical or different substituents R 11 substituted C r C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -0- (C r C 4 -alkyl), -S- (C r C 4 -alkyl) or -S (0) - (C r C 6 -alkyl), or together with the carbon atom to which they are attached, form an optionally mono- or polysubstituted, identically or differently, by halogen, oxygen, cyano or C 1 -C -alkyl-substituted cycle (preferably a saturated, unsaturated or partially unsaturated monocycle) with 3, preferably 5 to 8 ring atoms, the cycle containing 1 to
  • R 15 and R 16 independently of one another identical or different hydrogen or -OH, or represents in each case optionally mono- or polysubstituted by R 11 substituted C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 -alkynyl, C 3 -C 8 -cycloalkyl, C 6 -C 14 -aryl, C 2 -C 9 -heterocyclyl or C 2 -C -heteroaryl or, together with the nitrogen atom to which they are attached, form a 3- to 7- membered ring which may contain another heteroatom not belonging to the nitrogen (directly) from the series N, O,
  • R 19 is H, C r C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 -alkynyl, -C (S) R 15, -
  • R 20 and R 21 independently of one another are each optionally mono- or polysubstituted by identical or different substituents by fluorine, chlorine, bromine, -OH or cyano-substituted C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl , C 2 -C 6 -alkynyl or for hydrogen, as well as agrochemically active salts thereof.
  • X 1 is CH or N, R 1 is each optionally mono- or polysubstituted by identical or different substituents R 7 -substituted phenyl or naphthalenyl,
  • R 2 is halogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl or hydrogen,
  • R 301 in each case optionally monosubstituted or polysubstituted by identical or different substituents R 8 Ci-C 6 alkyl, C 2 -C 6 alkenyl, C 3 - 6 allenyl, C 2 -6-alkynyl, C 3 -C 8 - Cycloalkyl, C 1 -C 6 -alkoxy, C 2 -C 9 -heterocyclyl, C 2 -C 9 -oxo-heterocyclyl, or heteroaryl,
  • R 401 is -NR 12 R 13 ,
  • R 5 and R 6 independently of one another represent hydrogen, fluorine, chlorine, bromine, cyano, nitro, or in each case optionally mono- or polysubstituted by identical or different substituents R 11 substituted C r C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -0- (C r C 4 - alkyl), S- (C r C 4 alkyl) or -S (0) - (C r C 6 alkyl), or taken together with the carbon atoms to which they are attached form an optionally mono- or multiply, identically or differently by halogen, oxygen,
  • R 7 is fluorine, chlorine, cyano, nitro, methyl, ethyl, isopropyl, -CF 3 , -CHF 2 , C 2 F 5 , CC1 3 ,
  • R 11 is substituted C 1 -C 6 -alkyl, C 2 -C 8 -alkenyl, C 1 -C 6 -alkynyl, C 3 -C 8 cycloalkyl, Ci-C 6 haloalkyl, C 2 -C 9 heterocyclyl, C 2 -C 9 - heteroaryl, -0- (Ci-C 4 alkyl), -S- (Ci-C 4 alkyl) , -O- (C 3 -C 8 -cycloalkyl), -S- (C 3 -
  • R 11 is -OH, fluorine, chlorine, bromine, cyano, -NH-C (0) R 20, -C (0) R 20, -C (0) OR 20, - C (O) NR 20 R 21 , -S0 2 R 20 or optionally monosubstituted or polysubstituted by identical or different fluorine, chlorine, bromine, -OH, cyano, Ci-C 6 alkyl or -0- (C r C 4 alkyl) substituted C 6 -alkyl, C 3 -C 8 - cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -0- (C r C 4 alkyl), -S- (C r C 4 alkyl) , -O- (C 3 -C 8 -cycloalkyl), -S- (C 3 -C 8 -cycloalkyl), -S- (C 3 -C 8 -cycloalkyl
  • R 19 is H, C 2 -C 6 -alkynyl, -C (O) R 15 , -SO 2 R 15 , -C (O) OR 15 ,
  • R 20 and R 21 independently of one another are each optionally mono- or polysubstituted by identical or different substituents C 1 -C 6 -alkyl substituted by fluorine, chlorine, -OH, cyano, C 3 -C 6 -alkyl,
  • Cycloalkyl C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or for hydrogen, and agrochemically active salts thereof.
  • X 1 is CH or N
  • R 1 represents optionally mono- or polysubstituted by identical or different substituents R 7 -substituted phenyl
  • R 2 is methyl, ethyl, isopropyl, cyclopropyl, or hydrogen
  • R 301 represents in each case optionally monosubstituted or polysubstituted by identical or different substituents R 8 substituted C 6 alkyl, C 2 -C 6 alkenyl, C 3 -C 6- alkenyl, C 2 -C 6 -alkynyl, C 3 -C 8 -cycloalkyl or C 1 -C 6 -alkoxy,
  • R 401 is -NR 12 R 13 ,
  • R 5 and R 6 are independently hydrogen, fluorine or cyano, or together with the carbon atoms to which they are attached form a
  • R 8 is fluorine, chlorine, cyano or in each case optionally mono- or polysubstituted by identical or different substituents R 11 -substituted C 1 -C 6 -alkyl, C 2 -C 8 -alkenyl, C 2 -C 8 -alkynyl, C 3 -C 8 cycloalkyl, C 6 -C 4 aryl, heterocyclyl, heteroaryl, -0- (C r C 4 alkyl), -S- (C r C 4 alkyl), -0- (C 3 -C 8 cycloalkyl ), -S- (C 3 -C 8 -cycloalkyl),
  • R 11 represents one or more of the following groups: -OH, fluorine, chlorine, bromine, cyano, -NH-
  • C (0) R 20, -C (0) R 20, -C (0) OR 20, -C (O) NR 20 R 21, -S0 2 R 2 ° is equal to or in each case optionally monosubstituted or polysubstituted or different manner by fluorine, chlorine, bromine, OH, cyano, C r C 6 alkyl or 0- (C r C 4 alkyl) substituted C r C 6 alkyl, C 3 -C 8 cycloalkyl, C 2 -C 6 alkenyl , C 2 -C 6 alkynyl, -0- (C r C 4 alkyl), -S- (C r C 4 alkyl), -O-
  • R 12 is: -C (S) R 15 , -C (O) R 15 , -SO 2 R 15 , -C (O) OR 15 , -OR 15 or -C (O) NR 15 R 16 ,
  • R 13 is C r C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, or hydrogen,
  • R 15 is in each case optionally mono- or polysubstituted by identical or different
  • R 16 is hydrogen, methyl, ethyl or propyl
  • R 19 is H, C 2 -C 6 -alkynyl, -C (O) R 15 , -SO 2 R 15 , -C (O) OR 15 ,
  • R 20 and R 21 independently of one another are each optionally mono- or polysubstituted by identical or different fluorine, chlorine, bromine, -OH, cyano-substituted methyl, ethyl, propyl, iso-propyl, cyclopropyl, cyclobutyl or hydrogen, and also agrochemically active salts from that.
  • N is N
  • 2-chloro-6-fluorobenzyl 1- (2-chlorophenyl) ethyl, 1- (3-chlorophenyl) ethyl, 1- (4-chlorophenyl) ethyl, 3-cyanobenzyl, 4-cyanobenzyl, 4- (difluoromethoxy) b enyl, 2-cyanobenzyl, 2- (3-chlorophenyl) ethyl, 2- (2-chlorophenyl) ethyl, 1-naphthylmethyl, (pyridine)
  • Ethyl, cyclopropyl, R is -C (S) R, -SO 2 R, -C (O) OR 15 or -C (O) R,
  • R 15 is in each case optionally mono- or polysubstituted by identical or different
  • R 19 is H, acetyl, ethoxycarbonyl, methoxycarbonyl, prop-2-yn-1-yl, but-2-yn-1-yl, and agrochemically active salts thereof.
  • X 1 stands for CH
  • R 1 is 4-fluorophenyl, 3-chlorophenyl, 2,6-difluorophenyl, 3-methylphenyl
  • R 2 is cyclopropyl, methyl, H, difluoromethoxy
  • R 401 is acetylamino, n-propionylamino, isobutyrylamino, (cyclopropylcarbonyl) amino,
  • 2-chloro-6-fluorobenzyl 1- (2-chlorophenyl) ethyl, 1- (3-chlorophenyl) ethyl, 1- (4-chlorophenyl) ethyl, 3-cyanobenzyl, 4-cyanobenzyl, 4- (difluoromethoxy) benzyl, 2-Cyanobenzyl, 2- (3-chlorophenyl) ethyl, 2- (2-chlorophenyl) ethyl, 1-naphthylmethyl, (pyridine)
  • R 401 is -NHR 12 , the remaining substituents having one or more of the meanings given above, and the agrochemically active salts thereof.
  • R 1 has the same meaning as the general or preferred
  • R 2 has the same meaning as the general or preferred
  • R 301 represents methyl, ethyl, 1-propyl, propan-2-yl, isobutyl, butan-2-yl, 2-methylpropyl, prop-2-yl
  • R 1 has the same meaning as the general or preferred
  • R 2 has the same meaning as the general or preferred
  • R 5 and R 6 have the same meaning as the general or preferred
  • R 7 has the same meaning as the general or preferred
  • R 19 has the same meaning as the general or preferred ones
  • R 20 and R 21 have the same meaning as the general or preferred
  • the compounds of the formulas [I-a] and [I-b] according to the invention may optionally be used as mixtures of various possible isomeric forms, in particular stereoisomers, such as. B. E and Z, threo and erythro, and optical isomers, but optionally also of tautomers. Both the E and the Z isomers, as well as the threo and erythro, and the optical isomers, any mixtures of these isomers, as well as the possible tautomeric forms claimed.
  • Optionally substituted groups may be monosubstituted or polysubstituted, with multiple substituents the substituents may be the same or different.
  • the compounds of the formula (I) have acidic or basic properties and can form salts with inorganic or organic acids or with bases or with metal ions, optionally also internal salts or adducts. If the compounds of the formula (I) bear amino, alkylamino or other basic-property-inducing groups, these compounds can be reacted with acids to form salts or are obtained directly as salts by the synthesis. If the compounds of the formula (I) bear hydroxy, carboxy or other groups which induce acidic properties, these compounds can be reacted with bases to form salts.
  • Suitable bases are, for example, hydroxides, carbonates, bicarbonates of the alkali and alkaline earth metals, in particular those of sodium, potassium, magnesium and calcium, furthermore ammonia, primary, secondary and tertiary amines having Ci-C rAlkyl groups, mono-, di- and trialkanolamines of Ci-C pAlkanolen, 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 NaHSÜ 4 and KHSO 4 .
  • Suitable organic acids are, for example, 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, saturated or mono- or di-unsaturated C 6 -C 20 -fatty acids, saturated or singly or doubly unsaturated C 6 -C 20 -alkylenedicarboxylic acids, alkylsulfuric monoesters, alkylsulfonic acids (straight-chain or branched alkyl radicals having 1 to 20 carbon atoms), arylsulfonic acids or aryldisulfonic acids (aromatic radicals such as phenyl and naphthyl which carry one or two sulfonic acid groups), alkylphosphonic acids ( Phosphonic acids having straight-chain or
  • 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 groups, in particular aluminum, tin and lead, and the first to eighth transition groups, 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.
  • Alkyl saturated, straight-chain or branched hydrocarbon radicals having 1 to 8 carbon atoms, for example (but not limited to) C r C 6 -alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl, 1, 1-dimethyl ethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, l, 2-dimethylpropyl, l-methylpentyl , 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1, 2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1 Ethy
  • Haloalkyl straight-chain or branched alkyl groups having 1 to 8 (preferably 1 to 6 and more preferably 1 to 4) carbon atoms (as mentioned above), wherein in these groups partially or completely the hydrogen atoms
  • Halogen atoms as mentioned above may be replaced, e.g. (but not limited to) C1-C3 haloalkyl such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, 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-trichloroethyl, pentafluoroethyl and 1, l, l-trifluoroprop-2-yl;
  • Cycloalkyl monocyclic saturated hydrocarbon groups having from 3 to 8 (preferably 3 to 6) carbon ring members, eg (but not limited to) cyclopropyl, cyclopentyl and cyclohexyl;
  • Halocycloalkyl monocyclic, saturated hydrocarbon groups having 3 to 8 (preferably 3 to 6) carbon ring members (as mentioned above), in which groups the hydrogen atoms may be partially or completely replaced by halogen atoms as mentioned above, for example (but not limited to) Fluorocyclopropyl, 2,2-difluorocyclopropyl, 3,3-difluorocyclobutyl, 2-fluorocyclopentyl, 3-fluorocyclopentyl;
  • Heterocyclyl three to fifteen-membered preferably three- to nine-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 or 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.
  • oxiranyl aziridinyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4- Imidazolidinyl, 1,4-oxadiazolidin-3-yl, 2,4-oxadiazolidin-5-yl, 4- Imidazo
  • OxoHeterocvclyl three to fifteen-membered preferably drei- to nine-membered saturated or partially unsaturated heterocycle, (as mentioned above), wherein in these groups the hydrogen atoms of one or more CH 2 groups can be replaced by one or more carbonyl groups, eg (but not b) Restrictive) 2-Oxooxetan-3-yl, 5-Oxotetrahydrofuran-3-y 1, 2-oxotetrahydrofuran-3-yl, 2,5-dioxotetrahydrofuran-3-yl, 5-oxo-2,5-dihydrofuran 3-yl, 2-oxo-2,5-dihydrofuran-3-yl, 5-oxopyrrolidin-3-yl, 2-oxopyrrolidin-3-yl, 5-oxopyrrolidin-2-yl), 3-oxopyrrolidin-2-yl and 4-0x0-3,4-dihydro-2H-pyran
  • Alkynyl straight or branched hydrocarbon groups having 2 to 8 (preferably 2 to 6) carbon atoms and a triple bond in any position, e.g. (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-
  • Aryl 6- to 14-membered, fully unsaturated carbocyclic ring system, for example, but not limited to, phenyl, 1-naphthyl, 2-naphthyl, 2-anthryl, 1-anthryl; Heteroaryl: 5 or 6-membered, completely unsaturated monocyclic ring system containing one to four heteroatoms from the group oxygen, nitrogen or sulfur, the ring contains a plurality of oxygen atoms, so these are not directly adjacent;
  • Alkoxy a straight-chain or branched alkoxy, preferably CI-C ⁇ alkoxy and more preferably a C1-C3 alkoxy, such as (but not limited to) methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy , 2-methylpropoxy or 1, 1-dimethylethoxy, in particular methoxy or ethoxy;
  • Alkylthio represents straight-chain or branched alkylthio, e.g. (but not limited to) methylthio, ethylthio, n- and i-propylthio, n-, i-, sec- and tert-butylthio, n-pentylthio and its isomers such as 1-, 2- and 3-methyl-butylthio ,
  • the alkylthio groups may be substituted by 1 to 3 halogen atoms (preferably chlorine and / or fluorine), e.g. (but not limited to) di- and trifluoromethylthio and difluorochloromethylthio.
  • Haloalkoxy represents a straight-chain or branched alkoxy radical in which one or more hydrogen atoms have been replaced by fluorine, chlorine or bromine, for example (but not limited to) -OCF 3 , -OCHF 2 . Preference is given to one to three substitutions by fluorine or chlorine.
  • Acyloxy represents a straight-chain, branched, cyclic, saturated or unsaturated acyloxy radical linked via the oxygen atom, e.g. (but not limited to) acetyloxy, propionyloxy, isobutyryloxy.
  • Heteroalkyl saturated or unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 10 (preferably 2 to 8) carbon atoms and at least one heteroatom, wherein not two heteroatoms may be directly adjacent.
  • the phenylpyri (mi) dinylazoles of the formulas [Ia] and [Ib] according to the invention can be prepared in different ways.
  • the compounds of the formulas [Ia] and [Ib] are summarized under the formula [I] because the methods according to the invention can be applied to both formulas.
  • the possible methods are first shown schematically. Unless otherwise indicated, the radicals indicated have the meanings given above.
  • the phenylpyri (mi) dinylazoles of the formula [I] according to the invention can be prepared by process A according to the following scheme.
  • a 7 R 15 , -OR 15
  • phenylpyri (mi) dinylazoles of the formula [Id] according to the invention can also be prepared by process B (Scheme 2)
  • R2b alkyl, cycloalkyl or aryl
  • R 4 b / 40i b HA
  • R 3b / 3oib alkyl, cycloalkyl
  • Z l eg Cl, Br, I, -OTos, OMs, -OH
  • R ao Q -N HC (S) R 15 , -NH-C (O) R 15 , -NH C (O) OR 15 , -NH-C (O) NR 15 R 16 ,
  • R xl eg hydrogen, alkyl, cycloalkyl, benzyl
  • R x2 eg alkyl, cycloalkyl, benzyl
  • Z e.g. Cl, Br, I, -OTos, OMs, -OH
  • R 4c / 401c z Q - NHR i - _ NHR 1 a
  • R xl eg hydrogen, alkyl, cycloalkyl, benzyl, heterocyclyl
  • R x2 eg alkyl, cycloalkyl, benzyl, heterocyclyl New are compounds of the formula [III]
  • R 5 , R 6 stands for H.
  • B (OR * ) 2 for example B (OiPr) 2 , B (OH) 2 in which the symbols R, R have the abovementioned general, preferred, particularly preferred, very particularly preferred or in particular preferred meanings,
  • R 1 has the preferred, particularly preferred, most preferred, most preferred or especially preferred meanings given above, as well as salts thereof,
  • New are, for example, the compounds of the type [V] listed in the following table:
  • R 1 has the abovementioned particularly preferred, very particularly preferred, most preferred or especially preferred meanings
  • R and R have the preferred, particularly preferred, most preferred, most preferred or especially preferred meanings given above
  • R 2 , R 4/401 , R 5 , R 6 and X 1 have the abovementioned general, preferred, particularly preferred, very particularly preferred, most preferred or especially preferred meanings.
  • New are, for example, compounds: in which
  • the given mass is the peak of the isotopic pattern of the [M + H] + ion with the highest intensity; if that was [MH] "Ion detected, the stated mass is characterized by 2.
  • PG is a protective group, such as tetrahydro-2H-pyran-2-yl or 2- (trimethylsilyl) ethoxy] methyl
  • Met 3 represents a substituted metal atom such as tributylstannyl, 4,4,5,5-tetramethyl-l, 3,2-dioxaborolane -2-yl, and salts thereof, for example, [XI-1]:
  • a compound of the general formula [XIV] is brominated and then provided with a protective group to obtain a compound of the formula [XIII].
  • This compound can be reacted in a C-C coupling reaction with a substrate of the formula [XV-a] to give a compound of the formula [XII].
  • This compound can be converted to a compound of the formula [XI] by reaction with a strong base and subsequent reaction with a boron or tin compound.
  • This compound is reacted in a C-C coupling reaction with substrates of the general formula [XVII] to give compounds of the formula [X].
  • this compound is deprotected, whereby a compound of the general formula [IX] is obtained.
  • the obtained pyrazole of the formula [IX] is then reacted with substrates of the type [XVI] to give the arylpyrazoles of the formula [I] according to the invention (Scheme 1).
  • a compound of the general formula [VIII] is brominated, and a compound of the formula [VII] is obtained. This is converted to a compound of the type [VI] by reaction with substrates of the type [XVI], which may give rise to mixtures of pyrazole regioisomers. These can be separated into the individual regioisomers by conventional methods, for example chromatographic methods.
  • the compounds of the general formula [VI] can be reacted in a C-C coupling with substrates of the formula [XV-a] to give compounds of the formula [I] (Scheme 1).
  • the pyrazole compounds of general formula [VI] can be converted to compounds of type [V] by reaction with a boronic ester.
  • compounds of the type [V] can be converted into the arylpyrazoles of the formula [I] according to the invention by reaction with a substrate of the formula [IV-b] in a C-C coupling reaction (Scheme 1).
  • pyrazoles of the formula [XXVII] are then reacted with substrates of the type [XVI] to give the arylpyrazoles of the formula [Id] according to the invention.
  • R 3/301 cyclopropyl
  • a compound of the formula [Id] can also be obtained by CC coupling reaction of a substrate of the formula [XXVII] with a cyclopropylboronic acid
  • Compounds of the general formula [Id] can also be obtained by direct reaction of a hydrazine derivative with substrates of the formula [XXVI].
  • the preparation of the compounds of general formula [Ie] can be carried out according to method C as follows: Compounds of general formula [IX-a] are either commercially available or can be prepared by Method A. The compounds of the formula [IX-a] are converted by halogenation reaction to give compounds of the formula [XXVIII]. The obtained pyrazoles of the formula [XXVIII] are then reacted with substrates of the type [XVI] to give compounds of the formula [XXIX].
  • the intermediates of the formula [XXIX] can also be reacted without deprotection step directly by C-C coupling reaction with a boronic acid derivative of the formula [XXX] to form the pyrazoles of the formula [I-e] according to the invention.
  • pyrazolinones [XXXII] are prepared starting from the corresponding ⁇ -ketoesters [XXXI] by reaction with hydrazines. These pyrazolones are converted by difluoromethylation according to methods known from the literature (Org. Lett. 2006, 8, 17, 3805-3808) into compounds of the type [XXXIII]. The compounds of the formula [XXXIII] are then reacted by halogenation reaction to give compounds of the formula [VI-b].
  • the preparation of the intermediates having the general formula [III] can alternatively also be carried out according to process F as follows: In a CC coupling reaction, intermediates of the type [VI] are reacted with substrates of the general formula [XV-aa], where Met 2 is a boronic acid ester. In the course of the reaction, by cleavage of the amino-protecting group, the free amine is formed, whereby the intermediates of the general formula [III] are obtained.
  • these compounds can be converted to compounds of general formula [IIIa] by removal of the amine substituents (eg, in the case of benzylamines by hydrogenation reaction).
  • These compounds [IIIa] are converted into the arylpyrazoles of the formula [Ig] according to the invention by reaction with substrates of the formula [II].
  • the bromine-substituted pyrazoles of the formula [VII] are either commercially available or can be prepared according to literature specifications.
  • a method of preparing suitable bromopyrazoles is, for example, the bromination of corresponding pyrazoles [VIII] (for example described in EP-A 1382 603) by reaction with N-bromosuccinimide in acetic acid.
  • a method of preparing suitable compounds of the formula [XVI] is, for example, the reaction of alcohols with methanesulfonyl chloride and triethylamine (Org. Lett. 2008, 10, 4425-4428) or by Appel reaction with triphenylphosphine and CCL t (eg described in Tetrahedron 2008, 64, 7247-7251).
  • bases which can be used for this reaction are, for example, lithium hexamethyldisilazides (LiHMDS), Potassium carbonate, cesium carbonate and sodium hydride.
  • LiHMDS lithium hexamethyldisilazides
  • the preferred base is sodium hydride.
  • at least 1 equivalent of base is used.
  • the preferred solvents are tetrahydrofuran and dichloromethane.
  • an acid scavenger / a base eg pyridine, diisopropylethylamine, triethylamine or commercially available polymeric acid scavengers
  • Ratio to the starting material of the general formula [VII] can be used. If the starting material is a salt, at least two equivalents of the acid scavenger are needed.
  • pyridine as solvent, it is possible to dispense with the addition of a further base analogously to the literature described (EP-A-1 000 062).
  • the reaction is usually carried out at temperatures of 0 ° C - 100 ° C and preferably at 20 ° C - 30 ° C, but it can also be carried out at 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.
  • compounds [VI] are separated from the reaction mixture by one of the usual separation techniques.
  • the compounds of the formula [VI] in which R 3/301 is not hydrogen may be pure regioisomers or a mixture of both possible regioisomers (where the group R 3 / 301 can occupy both positions on the N atom of the pyrazole) can be obtained.
  • mixtures of regioisomers are obtained, they can be purified by physical methods (such as crystallization or chromatography methods) or, if appropriate, can also be used in the next step without prior purification.
  • any of ordinary solvents which are inert under the reaction conditions e.g. Sulfoxides (e.g., dimethylsulfoxide), cyclic ethers (e.g., dioxanes), and amides (e.g., N, N-dimethylformamide) can be used, and the reaction can be carried out in mixtures of two or more of these solvents.
  • Sulfoxides e.g., dimethylsulfoxide
  • cyclic ethers e.g., dioxanes
  • amides e.g., N, N-dimethylformamide
  • reaction time varies depending on the scale of the reaction and the reaction temperature, but is generally between one hour and 16 hours.
  • Other literature-described synthetic methods can also be used to prepare the compounds of formula [V].
  • compounds of formula [V] can be prepared by metalation of the bromopyrazoles [VI] with bases such as. n-butyllithium and reaction with boronic acid esters, e.g. Trimethyl borate and subsequent reaction of the resulting pyrazole boronic acid with pinacol (see, e.g., J. Het. Chem., 2004, 41, 931-940 or EP-A-1 382 603 and WO2007 / 16392).
  • Compounds of the formula [III] can be prepared, for example, by coupling the pyrazoleboronic acids [V] with heterocycles of the formula [IV-a] (where Z 2 represents a leaving group such as Cl or Br) in the presence of a catalyst, a base and a suitable solvent produce suitable temperatures according to known literature specifications ⁇ Top. Curr. Chem. 2002, 219, 11; Organomet. Chem. 1999, 28, 147 and references cited therein).
  • the carboxylic acids [L] are known or can be prepared from commercially available precursors according to literature specifications (see, for example, EP-A-1 650 194), for example from the commercially available pyridine-2-carboxylic acid by reaction with thionyl chloride in dimethylformamide.
  • compounds of the general formula [L] can also be prepared by oxidation of commercially available 4-halo-2-methylpyridine derivatives by literature procedures (Aust. J. Chem. 1982, 35, 2025-2034).
  • hydroxy compounds [LI] are known or can be prepared from commercially available precursors according to literature specifications (Chem. Pharm. Bull. 2003, 51, 8, 975-977).
  • solvents for the synthesis of compounds of formula [III] all conventional, inert solvents under the reaction conditions, such as alcohols (eg, methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, 1-butanol, 2-butanol, tert Butanol), cyclic and acyclic ethers (diethyl ether, dimethoxymethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, diisopropyl ether, tert-butyl methyl ether), aromatic hydrocarbons (eg benzene, toluene, Xylene), hydrocarbons (eg hexane, isohexane, heptane, cyclohexane), ketones (eg
  • Bases which are preferably used in the process according to the invention are alkali and alkaline earth metal hydroxides, alkali and alkaline earth metal carbonates, alkali metal hydrogencarbonates, alkali metal and alkaline earth metal acetates, alkali metal and alkaline earth metal alkoxides, and primary, secondary and tertiary amines.
  • Preferred bases are alkali metal carbonates such as e.g. Cesium carbonate, sodium carbonate, potassium carbonate.
  • the base is preferably used in the process according to the invention in a proportion of 100 to 1000 mol%, based on the aromatic boronic acid.
  • the preferred proportion is 600 to 800 mol%.
  • catalysts z. B Palladium metal, palladium compounds and / or nickel compounds are used.
  • the catalysts may also be supported on a solid support, such as activated carbon or alumina.
  • the amount of catalyst based on the leaving group Z 2 bearing heteroaromatic [IV-a], preferably 0.001 to 0.5 mol% and particularly preferably 0.01 to 0.2 mol%.
  • the catalyst may contain phosphorus-containing ligands or phosphorus-containing ligands may be added separately to the reaction mixture.
  • Suitable phosphorus 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 can connect the Phosphorgrappen several phosphines, wherein a part of this linkage may also be a metal atom.
  • Particularly preferred are phosphines such as triphenylphosphine, tri-tert-butylphosphane, tricyclohexylphosphane.
  • the educts, the solvent, the base, the catalyst and optionally the ligand are conveniently mixed and preferably reacted at a temperature of 0 ° C. to 200 ° C., particularly preferably at 100 ° to 170 ° 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.
  • the reaction can also be carried out in such a way that the various reactants are added in a controlled manner during the course of the reaction, with different dosing variants being possible.
  • the molar reactant ratio of the heteroaromatic [IV-a] to the organoboron compound [V] is preferably 0.9 to 1.5.
  • the processes according to the invention are generally carried out under normal pressure. However, it is also possible to work under elevated or reduced pressure.
  • the reaction is generally carried out using a shielding gas such as argon or nitrogen.
  • the catalyst obtained as a solid is separated by filtration, the crude product is freed from the solvent or solvents and then according to those skilled in the known and the respective product appropriate methods, eg. B. by recrystallization, distillation, sublimation, zone melting, melt crystallization or chromatography.
  • any of ordinary solvents which are inert under the reaction conditions e.g. cyclic and acyclic ethers (eg diethyl ether, tetrahydrofuran, dioxanes), aromatic hydrocarbons (eg benzene, toluene, xylene), halogenated hydrocarbons (eg dichloromethane, chloroform, carbon tetrachloride), halogenated aromatic hydrocarbons (eg chlorobenzene, dichlorobenzene) and nitriles (eg acetonitrile) can be used or the reaction can be carried out in mixtures of two or more of these solvents.
  • the preferred solvents are tetrahydrofuran and dichloromethane.
  • At least one equivalent of an acid scavenger / base e.g., Hunig base, triethylamine, or commercially available polymeric acid scavengers
  • the starting material is a salt, at least two equivalents of the acid scavenger are needed.
  • the reaction is usually carried out at temperatures of 0 ° C - 100 ° C and preferably at 20 ° C - 30 ° C, but it can also be carried out at 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 are, for example, peptide coupling reagents (for example, N- (3-dimethylaminopropyl) -N'-ethyl-carbodiimide mixed with 4-dimethylamino-pyridine, N- (3-dimethylaminopropyl) -N'-ethyl-carbodiimide mixed with 1 Hydroxybenzotriazole, bromo-tripyrrolidinophosphonium hexafluorophosphate, O- (7-azabenzotriazol-1-yl) -N, N, N ', N'-tetramethyl-uronium hexafluorophosphate, etc.).
  • peptide coupling reagents for example, N- (3-dimethylaminopropyl) -N'-ethyl-carbodiimide mixed with 4-dimethylamino-pyridine, N- (3-dimethylaminopropyl) -N'
  • a base such as e.g. Triethylamine or Hünig base can be used in the reaction.
  • the solvent there may be used any of ordinary solvents which are inert under the reaction conditions, e.g. Alcohols (eg, methanol, ethanol, propanol), cyclic and acyclic ethers (eg, diethyl ether, tetrahydrofuran, dioxanes), aromatic hydrocarbons (eg, benzene, toluene, xylene), halogenated hydrocarbons (eg, dichloromethane, chloroform, carbon tetrachloride), halogenated aromatic hydrocarbons (eg Chlorobenzene, dichlorobenzene), nitriles (eg, acetonitrile), and amides (eg, N, N-dimethylformamide, ⁇ , ⁇ -dimethylacetamide), or the reaction can be carried out in mixtures of two or more of these solvents.
  • the preferred solvent is dichloromethane.
  • the reaction is usually carried out at temperatures of 0 ° C - 100 ° C and preferably at 0 ° C - 30 ° C, but it may also be carried out at 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.
  • the compounds [Ic] are separated from the reaction mixture by one of the usual separation techniques. If necessary, the compounds are purified by recrystallization, distillation or chromatography.
  • Compounds of the formula [Ic] can be prepared, for example, by coupling the pyrazoleboronic acids [V] with heterocycles of the formula [IV-c] (where Z 2 is a leaving group, for example Cl or Br) in the presence of a catalyst, a base and a suitable solvent at appropriate temperatures according to known literature specifications ⁇ Top. Curr. Chem. 2002, 219, 11; Organomet. Chem. 1999, 28, 147 and references cited therein).
  • aminoheterocycles [XX] (in which X 1 is CH) are known or can be prepared by splitting off the N-BOC protective group from compounds of the formula [IV-a] according to literature specifications ⁇ Aust. J. Chem. 1982, 35, 10, 2025-2034 and references therein).
  • the catalyst obtained as a solid is separated by filtration, the crude product is freed from the solvent or solvents and then according to those skilled in the known and the respective product appropriate methods, eg. B. by recrystallization, distillation, sublimation, zone melting, melt crystallization or chromatography.
  • Compounds of the formula [I] can be prepared, for example, by coupling the halopyrazoles [VI] with metallated heterocycles of the formula [XV-a] (where Met 1 is a boronic ester or boronic acid, for example B (OiPr) 3 , B (OH) 2 ) in the presence of a catalyst, a base, optionally a ligand and a suitable solvent at suitable temperatures according to known literature procedures (Top Curr Curr 2002, 219, 11, Organomet Chem 1999, 28, 147 and literature cited therein, 2005 , 7, 21, 4753-4756).
  • Met 1 is a boronic ester or boronic acid, for example B (OiPr) 3 , B (OH) 2
  • compounds of the formula [I] can be prepared, for example, by coupling the halopyrazoles [VI] with metallated heterocycles of the formula [XV-a] in the presence of a catalyst, optionally an inorganic or organic halide salt, optionally a ligand and a suitable solvent at appropriate temperatures according to known literature specifications (see Synthesis 1992, 803-815).
  • a catalyst optionally an inorganic or organic halide salt, optionally a ligand and a suitable solvent at appropriate temperatures according to known literature specifications (see Synthesis 1992, 803-815).
  • Compounds of formula [XV-al] (wherein X 1 is CH) are commercially available or can be prepared according to literature procedures.
  • a method for preparing suitable haloheterocycles [XV-al] is the reaction of haloheterocycles of the formula [XXI] with bispinacolato diboron in the presence of a catalyst (such as Pd (OAc) 2, PdC dppf)), optionally a ligand (such as l, 3 bis (2,6-diisopropylphenyl) -4,5-dihydroimidazolium chloride), a base (such as potassium acetate, sodium acetate) and a solvent (such as tetrahydrofuran, dimethyl sulfoxide) by literature methods (Bioorg. Med. Chem. Lett. 2006, 16, 5, 1277-1281 and WO 04/014913) (Scheme 13).
  • Scheme 13 Scheme 13
  • compounds of the formula [XV-al] (in which X 1 is CH) can also be prepared by other methods known from the literature.
  • One method for preparing suitable heterocycles [XV-al] is to metallate the halopyridine [XXI] with a base (such as n-butyllithium) in a solvent (such as diethyl ether or tetrahydrofuran) followed by reaction with a boronic ester (such as B (e.g. i-PrO) 3 or B (OMe) s) and pinacol according to literature methods (Synthesis 2004, 4, 469-483 and literature described therein) (Scheme
  • compounds of the formula [XV-a2] can also be prepared by other methods known from the literature.
  • One method of preparing suitable haloheterocycles [XV-a2] is to metallate the halopyridine [XXII] using a metalating reagent (an alkyl lithium compound such as n-butyl lithium or a Grignard reagent such as isopropyl magnesium chloride) in a solvent (such as dimethyl) ethers or tetrahydrofuran) and subsequent reaction with a trialkyltin halide compound (such as, for example, BusSnCl) according to methods known from the literature (WO 08/008747 or Tetrahedron 1994, 275-284 and literature described therein) (Scheme 16).
  • a metalating reagent an alkyl lithium compound such as n-butyl lithium or a Grignard reagent such as isopropyl magnesium chloride
  • a solvent such as dimethyl
  • ALK C r C 5 alkyl
  • solvents for the reaction of compounds of the formula [XV-a] it is possible to use all customary solvents which are inert under the reaction conditions, e.g. cyclic and acyclic ethers (diethyl ether, dimethoxymethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, diisopropyl ether, tert-butyl methyl ether), aromatic hydrocarbons (eg benzene, toluene, xylene), amides (eg dimethylformamide, dimethylacetamide, 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 diethyl ether, dimethoxymethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, diisoprop
  • Halide salts for the reaction of compounds of the formula [XV-a] which are preferably used in the process according to the invention are e.g. Copper halides (e.g., CuBr or Cul), cesium halides (CsF), and tetraalkylammonium halides (TBAF).
  • Copper halides e.g., CuBr or Cul
  • cesium halides CsF
  • TBAF tetraalkylammonium halides
  • the halide salts are preferably used in the process according to the invention in a proportion of 1 to 400 mol%, based on the organic tin compound. However, it is also possible to use mixtures of the halide salts in proportions of from 1 to 400 mol%. Particularly preferred is the addition of a mixture of copper iodide and cesium fluoride in proportions of 1 - 200 mol%.
  • the amount of catalyst is based on the leaving group Met 1- bearing heteroaromatic [XV-a], preferably from 0.001 to 0.5 mol% and particularly preferably from 0.01 to 0.2 mol / o.
  • the catalyst may contain phosphorus-containing or arsenic-containing ligands, or phosphorus-containing or arsenic-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, wherein the three substituents on the phosphorus may be the same or different, may be chiral or achiral, and wherein one or more substituents may link the phosphorus groups of a plurality of phosphines, wherein a part of this linkage may also be a metal atom.
  • phosphines such as triphenylphosphine, tri-tert-butylphosphane, tricyclohexylphosphane.
  • Suitable arsenic ligands are, for example, tri-n-alkylarsans and triarylarsans, where the three substituents on the arsenic may be identical or different.
  • the total concentration of ligands based on the leaving group Met 1 bearing heteroaromatic [XV-a], preferably to 1 mol%, more preferably 0.01 to 0.5 mol%.
  • the starting materials, the solvent, the halide salt, the catalyst and optionally the ligand are conveniently mixed and preferably reacted at a temperature of 0 ° C.-200 ° C., more preferably at 60-150 ° 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. Apart from a one-pot reaction, the reaction can also be carried out in such a way that the various reactants are added in a controlled manner during the course of the reaction, with different dosing variants being possible.
  • the processes according to the invention are generally carried out under normal pressure. However, it is also possible to work under elevated or reduced pressure.
  • the reaction is generally carried out using a shielding gas such as e.g. Argon or nitrogen carried out.
  • the molar reactant ratio of halopyrazole [VI] to organotin compound [XV-a2] is preferably 0.9 to 2.
  • the catalyst obtained as a solid is separated by filtration, the crude product is freed from the solvent or solvents and then according to the expert known and the j ehren appropriate product methods, eg. B. by recrystallization, distillation, sublimation, zone melting, melt crystallization or chromatography.
  • Compounds of the formula [I] can be prepared, for example, by coupling the pyrazoleboronic acids [V] with heterocycles of the formula [IV-b] (where Z 2 represents a leaving group such as Cl or Br) in the presence of a catalyst, a base and a suitable solvent at suitable Prepare temperatures according to known literature procedures (Top Curr Curr 2002, 219, 11, b - A. Suzuki, Organomet Chem 1999, 28, 147 and references cited therein).
  • the pyridine N-oxides [XVIII] are known or can be obtained by oxidation of the corresponding pyridines (eg with H 2 O 2 , H 2 O 2 + methyltrioxorhenium, m-chloroperoxybenzoic acid, dimethyldioxirane or H 2 O 2 + manganese tetrakis (2,6 dichlorophenyl) porphyrin) according to literature specifications (ARKIVOC 2001 (i) 242-268 and references therein).
  • halogenated heterocycles [IV-bl] Another method for preparing suitable halogenated heterocycles [IV-bl] is the reaction of the 4-hydroxy-pyridine compounds [XIX] with halogenating agents (eg PCL, POCL) according to the literature (Pol J. Chem. 1981, 55, 4, 925 - 929) (Scheme 18).
  • halogenating agents eg PCL, POCL
  • hydroxypyridines [XIX] are known.
  • Compounds of the formula [IV-b2] (in which X 1 is CH) can be prepared according to literature procedures (Scheme 19).
  • One method for preparing suitable haloheterocycles [IV-b2] is the reaction of aminoheterocycles of the formula [XX] with trifluoromethyl ketones in the presence of titanium (IV) chloride, a base and a solvent (J. Am. Chem. Soc. 1996, 118, 7134-7138).
  • the imine formed in the course of this reaction can be converted into the amine [IV-b2] by reduction according to literature instructions ⁇ Tetrahedron 2009, 65, 9807-9813).
  • step (V3) for the C-C coupling of compound of formula [V].
  • the catalyst obtained as a solid is separated by filtration, the crude product is freed from the solvent or solvents and then according to those skilled in the known and the respective product appropriate methods, eg. B. by recrystallization, distillation, sublimation, zone melting, melt crystallization or chromatography.
  • halogenating agent e.g. N-bromosuccinimide and bromine are used.
  • solvents for the halogenation reaction it is possible to use all customary solvents which are inert under the reaction conditions, for example amides (for example dimethylformamide, dimethylacetamide, N-methylpyrrolidone), halogenated hydrocarbons (for example dichloromethane, chloroform, carbon tetrachloride), and acetic acid, or the reaction can be carried out in mixtures be carried out by two or more of these solvents.
  • the choice of solvents may vary depending on the halogenating reagent used.
  • the preferred solvents are acetic acid and dimethylformamide.
  • the halogenation reaction is usually carried out at temperatures of 0 ° C - 100 ° C and preferably at 20 ° C - 30 ° C.
  • reaction time varies depending on the scale of the reaction and the reaction temperature, but is generally between a few minutes and 48 hours.
  • the crude products are separated from the reaction mixture by one of the usual separation techniques. If necessary, the compounds are purified by recrystallization, distillation or chromatography or may optionally also be used directly for further reaction without prior purification.
  • the resulting bromopyrazoles [XXIV] are protected by heating in 3,4-dihydro-2H-pyran in the presence of a catalytic amount of Lewis acid (e.g., p-toluenesulfonic acid) on the nitrogen atom.
  • Lewis acid e.g., p-toluenesulfonic acid
  • the resulting products can occur as regioisomers. If necessary, the compounds are purified by distillation or chromatography or may optionally be used directly for further reaction without prior purification.
  • Compounds of the formula [XII] can be prepared, for example, by coupling the halopyrazoles [XIII] with metallated heterocycles of the formula [XV-a] (where Met is a boronic ester or boronic acid, for example B (OiPr) 3 , B (OH) 2 ) Presence of a catalyst, a base, optionally a ligand and a suitable solvent at suitable temperatures according to known literature specifications ⁇ Top. Curr. Chem. 2002, 219, 11; Organomet. Chem. 1999, 28, 147 and references cited therein, Org. Lett. 2005, 7, 21, 4753-4756).
  • Met is a boronic ester or boronic acid, for example B (OiPr) 3 , B (OH) 2
  • Presence of a catalyst, a base, optionally a ligand and a suitable solvent at suitable temperatures according to known literature specifications ⁇ Top. Curr. Chem. 2002, 219, 11; Organomet
  • Compounds of formula [XII] can also be e.g. by coupling the halopyrazoles [XIII] with metallated heterocycles of the formula [XV-a], in the presence of a catalyst, optionally an inorganic or organic halide salt, optionally a ligand and a suitable solvent at suitable temperatures according to known literature procedures (see Synthesis 1992, 803-815).
  • step (V6) The preparation of the compounds of the type [XV-a] is described in step (V6) for the analogous reaction of the halopyrazoles [VI].
  • One method of preparing the compounds of formula [XI] is to metallate the protected pyrazole [XII] with a base (such as n-butyllithium) in a solvent (such as diethyl ether or tetrahydrofuran) followed by reaction with a boronic ester (such as B (i-PrO) 3 or B (OMe) s) and pinacol by literature methods (see Tetrahedron Letters 2006, 47, 27, 2006, 4665-4669 and literature described therein) or with a trialkyltin halide compound (such as BusSnCl) analogous to literature methods (WO 06/108591)
  • the solvent there may be used any of ordinary solvents which are inert under the reaction conditions, e.g. cyclic and acyclic ethers (e.g., diethyl ether, tetrahydrofuran, dioxanes) may be used, or the reaction may be carried out in mixtures of two or more of these solvents.
  • cyclic and acyclic ethers e.g., diethyl ether, tetrahydrofuran, dioxanes
  • the preferred solvent is tetrahydrofuran.
  • the reaction is usually carried out at temperatures from -80 ° C to 0 ° C and preferably at -78 ° C to -20 ° C.
  • a change in the reaction temperature may be beneficial or necessary to ensure the reaction with the second reactant (e.g., the alkyltin halide or the boric acid ester).
  • 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.
  • reaction mixture can also be concentrated without aqueous workup and the crude products [XI] are distilled out directly from the reaction mixture.
  • Compounds of the formula [X] can be prepared, for example, by coupling the pyrazoles of the formula [XI] (where Met is a boronic ester or boronic acid such as B (OiPr) 3 , B (OH) 2 ) with compounds of the formula [XVII] (where Z 4 is a leaving group such as Cl, Br, I, mesylate or triflate) in the presence of a catalyst, a base, optionally a ligand and a suitable solvent at suitable temperatures according to known literature procedures produce ⁇ Top. Curr. Chem. 2002, 219, 11; Organomet. Chem. 1999, 28, 147 and references cited therein, Org. Lett. 2005, 7, 21, 4753-4756).
  • Met is a boronic ester or boronic acid such as B (OiPr) 3 , B (OH) 2
  • Z 4 is a leaving group such as Cl, Br, I, mesylate or triflate
  • Compounds of the formula [X] can also be obtained, for example, by coupling the pyrazoles of the formula [XI] (where Met 3 represents a tin-alkyl-bearing group such as -Sn (Bu) 3) with compounds of the formula [XVII] (where Z 4 is a Leaving group such as Cl, Br, I, mesylate or triflate) in the presence of a catalyst, optionally an inorganic or organic halide salt, optionally a ligand and a suitable solvent at suitable temperatures according to known literature specifications produce (see Synthesis 1992, 803- 815).
  • the choice of solvent, base, temperature, catalyst and optionally added ligand may vary depending on the pyrazole [XI] used and comprises the variations described in step (V6) b.
  • the processes according to the invention are generally carried out under normal pressure. However, it is also possible to work under elevated or reduced pressure.
  • the reaction is generally carried out using a shielding gas such as argon or nitrogen.
  • a shielding gas such as argon or nitrogen.
  • the molar reactant ratio of the pyrazole [XI] to the compound of the formula [XVII] is preferably 0.9 to 2.
  • the catalyst obtained as a solid is separated by filtration, the crude product is freed from the solvent or solvents and then according to those skilled in the known and the respective product appropriate methods, eg. B. by recrystallization, distillation, sublimation, zone melting, melt crystallization or chromatography.
  • 2- (trimethylsilyl-ethoxy) methyl and tetrahydropyran-2-yl protecting groups may e.g. in acidic medium (for example with methanolic HCl or trifluoroacetic acid) are removed according to literature rules (WO 03/099822 and J. Org Chem. 2008, 73, 4309 ⁇ 312 and literature contained therein).
  • Benzylic protecting groups may be removed by hydrogenolysis with a source of hydrogen (e.g., hydrogen, ammonium formate, formic acid or cyclohexene) in the presence of a catalyst (e.g., palladium on charcoal or palladium hydroxide on charcoal) according to literature procedures (EP-A-1 228 067).
  • Suitable solvents are all customary solvents which are inert under the reaction conditions, for example alcohols (for example methanol, ethanol, propanol), cyclic and acyclic ethers (for example diethyl ether, tetrahydrofuran, dioxanes), aromatic hydrocarbons (for example benzene, toluene, xylene), halogenated hydrocarbons (eg dichloromethane, chloroform, carbon tetrachloride), halogenated aromatic hydrocarbons (eg chlorobenzene, dichlorobenzene), nitriles (eg acetonitrile), carboxylic esters (eg ethyl acetate), amides (eg N, N-dimethylformamide, ⁇ , ⁇ -dimethylacetamide), dimethylsulfoxide, l , 3-dimethyl-2-imidazolinone, water and acetic acid, or the reaction can be carried out in mixtures of
  • the reaction is usually carried out at temperatures of 0 ° C-150 ° C, and preferably at room temperature, but it may also be carried out at the reflux temperature of the reaction mixture.
  • the reaction time varies depending on the scale the reaction and the reaction temperature, but is generally between half an hour and 72 hours.
  • the compounds [IX] are separated from the reaction mixture by one of the usual separation techniques. If necessary, the compounds are purified by recrystallization, distillation or chromatography or, if desired, may also be used in the next step without prior purification. It is also possible to isolate the compound of general formula [IX] as a salt, e.g. as a salt of hydrochloric acid or trifluoroacetic acid.
  • the compounds [I] are separated from the reaction mixture by one of the usual separation techniques.
  • the compounds of the formula [I] in which R 3 is not hydrogen may be pure regioisomers or a mixture of both possible regioisomers (where R 3/301 both positions can take on the N atom of the pyrazole) can be obtained.
  • mixtures of regioisomers are obtained, they can be purified by physical methods (such as crystallization or chromatography methods).
  • Bases which are preferably used in the process of the invention are alkali metal alkoxides (such as KOtBu or NaOtBu), lithium amides (such as LDA or LiHMDS) or metal hydrides (such as KH or NaH).
  • alkali metal alkoxides such as KOtBu or NaOtBu
  • lithium amides such as LDA or LiHMDS
  • metal hydrides such as KH or NaH
  • the solvent there may be used any of ordinary solvents which are inert under the reaction conditions, e.g. cyclic and acyclic ethers (eg diethyl ether, tetrahydrofuran, dioxanes, dimethoxyethane), amides (eg N, N-dimethylformamide, ⁇ , ⁇ -dimethylacetamide), dimethyl sulfoxide or HMPT can be used or the reaction can be carried out in mixtures of two or more of these solvents ,
  • polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide or HMPT is preferred.
  • the reaction is usually carried out at temperatures from -78 ° C to the boiling point of the solvent, preferably in the range of -20 ° C to 40 ° C.
  • the reaction time varies depending on the scale of the reaction and the reaction temperature, but is generally between half an hour and 72 hours.
  • the compounds [XXV] are separated from the reaction mixture by one of the usual separation techniques. If necessary, the compounds are purified by recrystallization, distillation or chromatography or, if desired, can also be used in the next step without prior purification.
  • the alkylpyridines or alkylpyrimidines of the formula [XXIV] are commercially available or can be prepared by methods known from the literature (for example WO 04/058776 or WO 04/035545).
  • the reaction is usually carried out at temperatures from -78 ° C to the boiling point of the solvent.
  • the reaction may be carried out in the presence of a base such as e.g. Triethylamine be performed.
  • a base such as e.g. Triethylamine be performed.
  • the solvent there may be used any of ordinary solvents which are inert under the reaction conditions, e.g. cyclic and acyclic ethers (e.g., tetrahydrofuran, dioxanes, dimethoxyethane) or alcohols (e.g., ethanol, methanol), or the reaction can be carried out in mixtures of two or more of these solvents.
  • cyclic and acyclic ethers e.g., tetrahydrofuran, dioxanes, dimethoxyethane
  • alcohols e.g., ethanol, methanol
  • polar solvents e.g. Ethanol is preferred.
  • the reaction is usually carried out at temperatures from 0 ° C to the boiling point of the solvent, preferably in the range of 25 ° C.
  • the reaction time varies depending on the scale of the reaction and the reaction temperature, but is generally between half an hour and 72 hours.
  • the reaction can be carried out in a microwave apparatus (e.g., CEM Explorer) at elevated temperature, which can shorten the reaction time required.
  • the reaction may be carried out in the presence of a base such as e.g. Triethylamine be performed.
  • a base such as e.g. Triethylamine be performed.
  • the solvent there may be used any of ordinary solvents which are inert under the reaction conditions, e.g. cyclic and acyclic ethers (e.g., tetrahydrofuran, dioxanes, dimethoxyethane) or alcohols (e.g., ethanol, methanol), or the reaction can be carried out in mixtures of two or more of these solvents.
  • cyclic and acyclic ethers e.g., tetrahydrofuran, dioxanes, dimethoxyethane
  • alcohols e.g., ethanol, methanol
  • polar solvents e.g. Ethanol is preferred.
  • the reaction is usually carried out at temperatures from 0 ° C to the boiling point of the solvent, preferably in the range of 25 ° C.
  • the reaction time varies depending on the scale of the reaction and the reaction temperature, but is generally between half an hour and 72 hours.
  • the reaction can be carried out in a microwave apparatus (e.g., CEM Explorer) at elevated temperature, which can shorten the reaction time required.
  • the reaction is carried out in the presence of a base (such as triethylamine, pyridine, sodium carbonate, potassium phosphate, cesium carbonate) and a Cu (II) salt (such as Cu (OAc) 2 or CuC.).
  • a base such as triethylamine, pyridine, sodium carbonate, potassium phosphate, cesium carbonate
  • a Cu (II) salt such as Cu (OAc) 2 or CuC.
  • reaction can be carried out with addition of a suitable ligand (such as pyridine or 2,2-bipyridine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylethylenediamine or 1,10-phenanthridine).
  • a suitable ligand such as pyridine or 2,2-bipyridine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylethylenediamine or 1,10-phenanthridine.
  • cyclic and acyclic ethers eg tetrahydrofuran, dioxanes, dimethoxyethane
  • haloalkanes eg dichloroethane
  • aromatic hydrocarbons eg benzene, toluene
  • haloalkanes such as dichloroethane is preferred.
  • the reaction is usually carried out at temperatures from 50 ° C to the boiling point of the solvent, preferably in the range of 70 ° C.
  • the reaction time varies depending on the scale of the reaction and the reaction temperature, but is generally between half an hour and 72 hours.
  • the reaction can be carried out in a microwave apparatus (e.g., CEM Explorer) at elevated temperature, which can shorten the reaction time required.
  • a microwave apparatus e.g., CEM Explorer
  • halogenating agent e.g. N-bromosuccinimide and bromine are used.
  • solvents for the halogenation reaction it is possible to use all customary solvents which are inert under the reaction conditions, e.g. Amides (e.g., dimethylformamide, dimethylacetamide, N-methylpyrrolidone), halogenated hydrocarbons (e.g., dichloromethane, chloroform, carbon tetrachloride), and acetic acid, or the reaction can be carried out in mixtures of two or more of these solvents.
  • Amides e.g., dimethylformamide, dimethylacetamide, N-methylpyrrolidone
  • halogenated hydrocarbons e.g., dichloromethane, chloroform, carbon tetrachloride
  • acetic acid e.g., acetic acid and dimethylformamide.
  • the halogenation reaction is usually carried out at temperatures from 0 ° C to 100 ° C, and preferably at 20 ° C to 80 ° 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.
  • the crude products are separated from the reaction mixture by one of the usual separation techniques. If necessary, the connections are through
  • the reaction is carried out in the presence of a base (such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate or cesium carbonate) and a palladium catalyst (such as dichloro [l, ferrocenyl bis (diphenylphosphine)] palladium (II) * CH 2 Cl 2 ).
  • a base such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate or cesium carbonate
  • a palladium catalyst such as dichloro [l, ferrocenyl bis (diphenylphosphine)] palladium (II) * CH 2 Cl 2
  • a base such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate or cesium carbonate
  • a palladium catalyst such as dichloro [l, ferrocenyl bis (diphenylphosphine)] palladium (II) * CH 2 Cl 2 .
  • the solvent there may be used any of ordinary solvents
  • the reaction is usually carried out at temperatures from 50 ° C to the boiling point of the solvent, preferably in the range of 90 ° C.
  • the reaction time varies depending on the scale of the reaction and the reaction temperature, but is generally between half an hour and 72 hours.
  • the reaction can be carried out in a microwave apparatus (eg CEM Explorer) at elevated temperature, whereby the required reaction time can be shortened.
  • the compounds [IX-b] are separated from the reaction mixture by one of the usual separation techniques. If necessary, the compounds are purified by recrystallization, distillation or chromatography.
  • the conditions for the coupling correspond to the conditions given in the above procedure (V20) without the removal of the group R 3/301 by deprotection reaction.
  • the compounds [I-e] are separated from the reaction mixture by one of the usual separation techniques. If necessary, the compounds are purified by recrystallization, distillation or chromatography.
  • the reaction may be carried out in the presence of an acid, e.g. Acetic acid are carried out.
  • an acid e.g. Acetic acid are carried out.
  • solvents it is possible to use all customary solvents which are inert under the reaction conditions, for example cyclic and acyclic ethers (for example tetrahydrofuran, dioxanes, Dimethoxyethane), alcohols (eg, ethanol, methanol) or esters (ethyl acetate), or the reaction can be carried out in mixtures of two or more of these solvents.
  • cyclic and acyclic ethers for example tetrahydrofuran, dioxanes, Dimethoxyethane
  • alcohols eg, ethanol, methanol
  • esters ethyl acetate
  • the reaction is usually carried out at temperatures from 0 ° C to the boiling point of the solvent, preferably at reflux.
  • the reaction time varies depending on the scale of the reaction and the reaction temperature, but is generally between half an hour and 72 hours.
  • the reaction can be carried out in a microwave apparatus (e.g., CEM Explorer) at elevated temperature, which can shorten the reaction time required.
  • Compounds of the general formula [XXXIII] are obtained by reaction of compounds of the general formula [XXXII] with halo-difluoromethane compounds (such as, for example, chlorodifluoromethane, sodium chlorodifluoroacetate) by methods known from the literature (eg US5861359, Org. Lett. 2006, 8, 17, 3805-3808) , The reaction is carried out in the presence of a base such as e.g. Potassium carbonate performed.
  • halo-difluoromethane compounds such as, for example, chlorodifluoromethane, sodium chlorodifluoroacetate
  • the solvent there may be used any of ordinary solvents which are inert under the reaction conditions, e.g. Amides (e.g., dimethylformamide, dimethylacetamide, N-methylpyrrolidone), cyclic and acyclic ethers (e.g., tetrahydrofuran, dioxanes, dimethoxyethane) or nitriles (e.g., acetonitrile).
  • Amides e.g., dimethylformamide, dimethylacetamide, N-methylpyrrolidone
  • cyclic and acyclic ethers e.g., tetrahydrofuran, dioxanes, dimethoxyethane
  • nitriles e.g., acetonitrile
  • halogenating agent for example, N-bromosuccinimide or bromine
  • solvents for the halogenation reaction it is possible to use all customary solvents which are inert under the reaction conditions, for example amides (for example dimethylformamide, dimethylacetamide, N-methylpyrrolidone), halogenated hydrocarbons (for example dichloromethane, chloroform, carbon tetrachloride) or acetic acid or the reaction can be carried out in mixtures of two or more of these solvents are carried out.
  • amides for example dimethylformamide, dimethylacetamide, N-methylpyrrolidone
  • halogenated hydrocarbons for example dichloromethane, chloroform, carbon tetrachloride
  • acetic acid for example dichloromethane, chloroform, carbon tetrachloride
  • the choice of solvents may vary depending on the halogenating reagent used.
  • the preferred solvents are dichloromethane and tetrach
  • the halogenation reaction is normally carried out at temperatures of 0 ° C - 100 ° C and preferably at 20 ° C - 80 ° 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.
  • the crude products are separated from the reaction mixture by one of the usual separation techniques. If necessary, the compounds are purified by recrystallization, distillation or chromatography or may optionally also be used directly for further reaction without prior purification.
  • the reaction is carried out in the presence of a Lewis acid e.g. Boron tribromide and a solvent inert under the reaction conditions (e.g., dichloromethane).
  • a Lewis acid e.g. Boron tribromide
  • a solvent inert under the reaction conditions (e.g., dichloromethane).
  • the reaction is usually carried out at temperatures of -20 ° C + 20 ° C, preferably at -5 ° C to 0 ° C.
  • Compounds of the formula [III] can be prepared, for example, by coupling the halopyrazoles [VI] with metallated heterocycles of the formula [XV-a] (where Met is a boronic ester or boronic acid, for example B (OiPr) 3 , B (OH) 2 ) Presence of a catalyst, a base, optionally a ligand and a suitable solvent at suitable temperatures according to known Chem., 2002, 219, 11; Organomet. Chem. 1999, 28, 147 and references cited therein, Org. Lett. 2005, 7, 21, 4753-4756).
  • Met is a boronic ester or boronic acid, for example B (OiPr) 3 , B (OH) 2
  • Presence of a catalyst, a base, optionally a ligand and a suitable solvent at suitable temperatures according to known Chem., 2002, 219, 11; Organomet. Chem. 1999, 28, 147 and references cited therein, Org.
  • step (V 6) The preparation of the compounds of the type [VI] is described in step (V 6).
  • step (V6) for the C-C coupling of compound of formula [VI].
  • m-chloroperbenzoic acid o O x one (Kaliumperoxomonosulfat) can be used.
  • solvents for the oxidation reaction it is possible to use all customary solvents which are inert under the reaction conditions, e.g. halogenated hydrocarbons (e.g., dichloromethane), ethers (e.g., tetrahydrofuran), alcohols (e.g., methanol) or water, or the reaction may be carried out in mixtures of two or more of these solvents.
  • the choice of solvents may vary depending on the oxidizing reagent used.
  • the preferred solvents are dichloromethane (m-CPBA) and water / THF mixtures (oxone).
  • the oxidation reaction is usually carried out at temperatures of 0 ° C to 20 ° C.
  • the reaction time varies depending on the scale of the reaction and the reaction temperature, but is generally between several hours and 48 hours.
  • the crude products are separated from the reaction mixture by one of the usual separation techniques. If necessary, the compounds are purified by recrystallization, distillation or chromatography or, if appropriate, can also be used directly for further reaction without prior purification.
  • the solvent there may be used any of ordinary solvents which are inert under the reaction conditions, e.g. Amides (e.g., dimethylformamide, dimethylacetamide, N-methylpyrrolidone), cyclic and acyclic ethers (e.g., tetrahydrofuran, dioxanes, dimethoxyethane), nitriles (e.g., acetonitrile), sulfoxides (e.g., dimethyl sulfoxide), or alcohols (e.g., ethanol, n-butanol).
  • the reaction may be carried out without solvent, e.g. when using an excess of amine.
  • the reaction is usually carried out at temperatures from 50 ° C to the boiling point of the solvent.
  • the reaction time varies depending on the scale of the reaction and the reaction temperature, but is generally between half an hour and 72 hours.
  • the reaction can be carried out in a microwave apparatus (e.g., CEM Explorer) at elevated temperature, which can shorten the reaction time required.
  • R xl is H and R x2 is benzyl, 4-methoxybenzyl, or 3,4-dimethoxybenzyl, according to literature methods (eg J. Med. Chem. 1999, 42, 12, 2180-2190 or Bioorg. Med. Chem. Lett 2008, 18, 14, 4006-4010).
  • the reaction is usually carried out in the presence of a strong acid, for example sulfuric acid, hydrochloric acid or trifluoroacetic acid.
  • a strong acid for example sulfuric acid, hydrochloric acid or trifluoroacetic acid.
  • the reaction is usually carried out at temperatures from 0 ° C up to 120 ° C.
  • the reaction time varies depending on the scale of the reaction and the reaction temperature, but is generally between half an hour and 72 hours.
  • the reaction can be carried out in a microwave apparatus (eg CEM Explorer) at elevated temperature, whereby the required reaction time can be shortened.
  • Another object of the invention relates to the non-medical use of phenylpyri (mi) dinylazoles invention or mixtures thereof for controlling unwanted microorganisms and for the reduction of mycotoxins in plants and parts of plants.
  • Another object of the invention relates to an agent for controlling unwanted microorganisms and for the reduction of mycotoxins in plants and parts of plants, comprising at least one Phenylpyri (mi) dinylazole according to the present invention.
  • the invention relates to a method for controlling unwanted microorganisms and for the reduction of mycotoxins in plants and parts of plants, characterized in that the phenylpyri (mi) dinylazoles invention are applied to the microorganisms and / or in their habitat.
  • the substances according to the invention have a strong microbicidal activity and can be used for controlling unwanted microorganisms, such as fungi and bacteria, in crop protection and in the protection of materials.
  • the phenylpyri (mi) dinylazoles of the formula (Ia) and (Ib) according to the invention have very good fungicidal properties and can be employed in crop protection, for example for controlling Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
  • Bactericides can be used in crop protection, for example, to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
  • the fungicidal compositions according to the invention can be used curatively or protectively for controlling phytopathogenic fungi.
  • the invention therefore also relates to curative and protective methods for controlling phytopathogenic fungi by the use of the active compounds or agents according to the invention, which are applied to the seed, the plant or plant parts, the fruits or the soil in which the plants grow.
  • the compositions of the invention for controlling phytopathogenic fungi in crop protection comprise an effective but non-phytotoxic amount of the active compounds according to the invention.
  • an effective but non-phytotoxic amount is meant 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 phytotoxicity symptoms It depends on several factors, for example on the fungus to be controlled, the plant, the climatic conditions and the ingredients of the agents according to the invention.
  • plants and parts of plants can be treated.
  • 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 aboveground and subterranean 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.
  • the plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.
  • 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, oranges 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. leek, onion), Papilionaceae sp.
  • 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 chol, kohlrabi radishes, rape, mustard, horseradish, and cress), Fabacae sp. (for example, bean, peanuts), Papilionaceae sp. (for example, soybean), Solanaceae sp. (for example potatoes), Chenopodiaceae sp.
  • 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
  • crop plants are treated according to the invention.
  • pathogens of fungal diseases which can be treated according to the invention are named:
  • 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, for example, Cochliobolus sativus (conidia form: woodturners, Syn: Helminthosporium); Colletotrichum species, such as Colletotrichum lindemuthanium; Cycloconium species such as cycloconium oleaginum; Slide types 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, such as Leptospha
  • 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
  • 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; Cladosporium species, such as 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;
  • Alternaria species such as Alternaria spp .
  • Aspergillus species such as Aspergillus flavus
  • Cladosporium species such as Cladosporium cladosporioides
  • Claviceps species such as Claviceps purpurea
  • Fusarium species such as Fusarium culmorum
  • Gibberella species such as Gibberella
  • 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
  • Botrytis species such as Botrytis cinerea
  • Rhizoctonia species such as Rhizoctonia solani
  • Helminthosporium 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:
  • 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).
  • Undesirable microorganisms in the present case are phytopathogenic fungi and bacteria.
  • the substances according to the invention can therefore be used to protect plants within a certain period of time after the treatment against the infestation by the said pathogens.
  • the period of time within which protection is afforded generally extends from 1 to 10 days, preferably 1 to 7 days after the treatment of the plants with the active ingredients.
  • the active compounds according to the invention can be used to combat cereal diseases, for example Erysiphe species, Puccinia and Fusarium species, rice diseases such as Pyricularia and Rhizoctonia and diseases in wine, fruit and vegetable cultivation , for example against Botrytis, Venturia, Sphaerotheca and Podosphaera species.
  • the active compounds according to the invention are also suitable for increasing crop yield. They are also low toxicity and have good plant tolerance.
  • the compounds according to the invention may also be used in certain concentrations or application rates as herbicides, safeners, growth regulators or agents for improving plant properties, or as microbicides, for example as fungicides, antimycotics, bactericides, viricides (including anti-viral agents) or as anti-MLO agents ( Mycoplasma-like-organism) and RLO (Rickettsia-like-organism). If appropriate, they can also be used as insecticides. If appropriate, they can also be used as intermediates or precursors for the synthesis of further active ingredients.
  • the active compounds according to the invention may optionally also be used in certain concentrations and application rates as herbicides, for influencing plant growth and for controlling animal pests. If appropriate, they can also be used as intermediates and precursors for the synthesis of further active ingredients.
  • the active compounds according to the invention are suitable for plant tolerance, favorable toxicity to warm-blooded animals 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.
  • the treatment according to the invention of the plants and plant parts with the active compounds or agents takes place directly or by acting on their environment, habitat or storage space according to the usual treatment methods, eg by dipping, spraying, spraying, sprinkling, evaporation, Spraying, atomizing, sprinkling, foaming, spreading, spreading, drenching, drip irrigation and, in the case of propagating material, in particular for seeds, further by dry pickling, wet dressing, slurry pickling, encrusting, single or multi-layer coating, etc. It is further It is 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 amount of active ingredient used can vary within a substantial range. It depends essentially on the type of effect desired. In general, the application rates are between 1 g and 10 kg of active ingredient per hectare of soil, preferably between 5 g and 5 kg per ha.
  • the beneficial effect of the crop plant compatibility of the active compounds according to the invention is particularly pronounced in certain concentration ratios.
  • the weight ratios of the active ingredients in the drug combinations can be varied in relatively large ranges.
  • 1 part by weight of active compound of the formula (I) accounts for 0.001 to 1000 parts by weight, preferably 0.01 to 100 parts by weight, particularly preferably 0.05 to 20 parts by weight of one of the above (b ') mentioned, the crops compatibility-improving compounds (antidotes / safener).
  • the active compounds according to the invention are generally used in the form of ready-to-use formulations.
  • the active substances contained in the active ingredient combinations can also be mixed in individual formulations in the application, i. in the form of tank mixes are used.
  • mycotoxins include: deoxynivalenol (DON), nivalenol, 15-Ac-DON, 3-Ac-DON, T2 and HT2 toxin, fumonisins, zearalenone, moniliformin, fusarin, diacetoxyscirpenol (DAS) , Beauvericin, enniatine, fusaroproliferin, fusarenol, ochratoxins, patulin, maternal alkaloids and aflatoxins, which may be caused, for example, by the following fungi: Fusarium spec., Such as Fusarium acuminatum, F.
  • 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 fungi.
  • Technical materials as used herein mean non-living materials that have been prepared for use in the art.
  • technical materials to be protected from microbial change or destruction by the active compounds of the invention may be adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastics, coolants, and other materials that may be infested or degraded by microorganisms .
  • materials to be protected are also parts of production plants, such as cooling water circuits, called, which can 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.
  • microorganisms that can cause degradation or a change in the technical materials, for example, bacteria, fungi, yeasts, algae and mucus organisms may be mentioned.
  • the active compounds according to the invention preferably act against fungi, in particular molds, wood-discolouring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.
  • microorganisms of the following genera Alternaria, such as Alternaria tenuis; Aspergillus, such as Aspergillus niger; Chaetomium, like Chaetomium globosum; Coniophora, like Coniophora puetana; Lentinus, like Lentinus tigrinus; Penicillium, such as Penicillium glaucum; Polyporus, such as Polyporus versicolor; Aureobasidium, such as Aureobasidium pullulans; Sclerophoma, like Sclerophoma pityophila; Trichoderma, such as Trichoderma viride; Escherichia, like Escherichia coli; Pseudomonas, such as Pseudomonas aeruginosa; Staphylococcus, such as Staphylococcus aureus.
  • Alternaria such as Alternaria tenuis
  • Aspergillus such as Asperg
  • the present invention further relates to an agent for controlling unwanted microorganisms, comprising at least one of the thienylaminopyrimidines according to the invention.
  • an agent for controlling unwanted microorganisms comprising at least one of the thienylaminopyrimidines according to the invention.
  • Preference is given to fungicidal compositions which contain agriculturally useful auxiliaries, solvents, carriers, surface-active substances or extenders.
  • 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 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 silicates, as solid carriers for granules: eg crushed 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 paper, sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfon
  • oligo- or polymers for example starting from vinylic monomers, from acrylic acid, from EO and / or PO alone or in combination with, for example, (poly) alcohols or (poly) amines.
  • lignin and its sulfonic acid derivatives simple and modified celluloses, aromatic and / or aliphatic sulfonic acids and their adducts with formaldehyde.
  • the active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, scattering granules, suspension-emulsion concentrates, active substance-impregnated natural products, active ingredient Impregnated synthetic materials, fertilizers and Feinstverkapselitch in polymeric materials.
  • solutions emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, scattering granules, suspension-emulsion concentrates, active substance-impregnated natural products, active ingredient Impregnated synthetic materials, fertilizers and Feinstverkapselitch in polymeric materials.
  • the active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom, such as ready-to-use solutions, emulsions, water- or oil-based suspensions, powders, wettable powders, pastes, soluble powders, dusts, soluble granules, scattering granules, suspension emulsion concentrates, Active substance-impregnated natural products, active ingredient-impregnated synthetic substances, fertilizers and Feinstverkapselitch be applied in polymeric materials. The application is done in a conventional manner, for example by pouring, spraying, spraying, scattering, dusting, foaming, brushing, etc.
  • the active ingredients can be applied by the ultra-low-volume method or the active ingredient preparation or the active ingredient itself in the Inject soil. It can also be the seed of the plants to be treated.
  • the formulations mentioned can be prepared in a manner known per se, for example by mixing the active compounds with at least one customary extender, solvent or diluent, emulsifier, dispersing and / or binding or fixing agent, wetting agent, water repellent, optionally siccatives and UV stabilizers and optionally dyes and pigments, defoamers, 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.
  • active ingredients such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides , Fertilizers, safeners or semiochemicals.
  • Excipients which can be used are those which are suitable for imparting special properties to the composition itself and / or preparations derived therefrom (for example spray liquor, seed dressing), such as certain technical properties and / or specific biological properties.
  • Typical auxiliaries are: extenders, solvents and carriers.
  • Suitable extenders include, for example, water, polar and non-polar organic chemical liquids, for example from the classes of aromatic and non-aromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), alcohols and polyols (which may also be substituted, etherified and / or esterified esters (also fats and oils) and (poly) ethers, simple and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, sulfones and sulfoxides (such as dimethyl sulfoxide).
  • aromatic and non-aromatic hydrocarbons such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes
  • alcohols and polyols which may also be substituted, etherified and / or esterified esters (also fats and oils) and (poly)
  • liquefied gaseous diluents or carriers are meant those liquids which are gaseous at normal temperature and under normal pressure, for example 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.
  • organic solvents can also be used as auxiliary solvents.
  • Suitable liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, eg petroleum fractions, alcohols such as butanol or glycol and their Ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water.
  • the fiction, contemporary means may additionally contain other ingredients, such as surface-active substances.
  • 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 alkyl taurates), phosphoric 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.
  • Colorants 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.
  • Other additives may be fragrances, mineral or vegetable optionally modified oils, waxes and nutrients (also trace nutrients), such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • Stabilizers such as cold stabilizers, preservatives, antioxidants, light stabilizers or other chemical and / or physical stability-improving agents may also be present.
  • additional components may also be included, e.g. protective colloids, binders, adhesives, thickeners, thixotropic substances, penetration enhancers, stabilizers, sequestering agents, complexing agents.
  • the active ingredients can be combined with any solid or liquid additive commonly used for formulation purposes.
  • the formulations generally contain between 0.05 and 99% by weight, 0.01 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 formulations described above can be used in a method according to the invention for controlling unwanted microorganisms, in which the thienylaminopyrimidines according to the invention are applied to the microorganisms and / or their habitat.
  • the active compounds according to the invention can also be used in admixture with known fungicides, bactericides, acaricides, nematicides or insecticides, so as to obtain e.g. to broaden the spectrum of action or to prevent development of resistance.
  • Suitable mixing partners are, for example, known fungicides, insecticides, acaricides, nematicides or bactericides (see also Pesticide Manual, 13th ed.) In question.
  • the application is done in a custom forms adapted to the application.
  • the control of phytopathogenic harmful fungi is carried out primarily by the treatment of the soil and the above-ground parts of plants with pesticides. Because of concerns about the potential impact of plant protection products on the environment and health There is an effort by humans and animals to reduce the amount of active substances applied.
  • the active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules.
  • the application is done in the usual way, e.g. by pouring, spraying, spraying, scattering, dusting, foaming, brushing, 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. It can also be the seed of the plants to be treated.
  • 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 applied by pouring or dropping 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;
  • soil treatment from 0.1 to 10,000 g / ha, preferably from 1 to 5,000 g / ha.
  • the compounds according to the invention can be used to protect against fouling of objects, in particular hulls, sieves, nets, structures, quay systems and signal systems, which come into contact with seawater or brackish water. Furthermore, the compounds according to the invention can be used alone or in combinations with other active substances as antifouling agents.
  • 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 outside is provided or assembled to the plant and which, when introduced into the nuclear genome, chloroplast genome or hypochondriacoma genome of the transformed plant, imparts new or improved agronomic or other properties by expressing a protein or polypeptide of interest or another gene found in the plant Plant or other genes that are present in the plant, down-regulated or switched off (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 defined by its specific presence in the plant genome is referred to as a transformation or transgenic event.
  • the treatment according to the invention can also lead to superadditive (“synergistic”) effects.
  • the following effects are possible, which go beyond the effects actually expected: reduced application rates and / or extended effect s spectrum 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 dryness or water or soil salt content, increased flowering efficiency, 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 crop, higher Sugar concentration in fruits, better shelf life and / or processability of harvested products.
  • phytopathogenic fungi, bacteria and viruses are understood to be undesirable phytopathogenic fungi and / or microorganisms and / or viruses.
  • the substances according to the invention can therefore be employed for the protection of plants against 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 stress factors, ie 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. B. based on improved plant physiology, improved plant growth and improved plant development, such as water efficiency, water retention efficiency, improved nitrogen utilization, increased carbon assimilation, improved photosynthesis, increased germination and accelerated Abreife.
  • the yield may be further influenced by improved plant architecture (under stress and non-stress conditions), including early growth, control of buds for hybrid seed production, seedling vigor, plant size, internode count and spacing, rooting , 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 heterosis or hybrid effect, which generally leads to higher yield, higher 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, i. H. Plants tolerant 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 which select for naturally occurring mutations of the above mentioned genes.
  • 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
  • HPPD hydroxyphenylpyruvate dioxygenases
  • HPPD inhibitors can be transformed with a gene encoding a naturally occurring resistant HPPD enzyme or a gene encoding a mutant 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.
  • Other herbicide-resistant plants are plants that have been tolerated to acetolactate synthase (ALS) inhibitors.
  • 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 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, ie plants which 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 as used herein includes any plant containing at least one transgene comprising a coding sequence encoding:
  • an insecticidal crystal protein from Bacillus thuringiensis or an insecticide part thereof such as the insecticidal crystal proteins available online at: http: // www. lifesci. sussex.ac.uk/Home/Neil Crickmore / Bt /, or insecticidal parts thereof, e.g. Proteins of the cry protein classes CrylAb, CrylAc, CrylF, Cry2Ab, Cry3Ae or Cry3Bb or insecticidal parts thereof; or
  • 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 insecticides of Bacillus thuringiensis crystal proteins, such as a hybrid of the proteins of 1) above or a hybrid of the proteins of 2) above, e.g. The protein CrylA.105 produced by the corn event MON98034 (WO 07/027777); or
  • VIPs vegetative insecticidal proteins
  • 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 VTP1A and VIP2A.
  • an insecticidal hybrid 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 are tolerant of abiotic stressors. Such plants can be obtained by genetic transformation or by selection of plants containing a mutation conferring such stress resistance.
  • Particularly useful plants with stress tolerance include the following: a. Plants containing a transgene capable of reducing the expression and / or activity of the poly (ADP-ribose) polymerase (PARP) gene in the plant cells or plants. b. Plants containing a stress tolerance-enhancing transgene capable of reducing the expression and / or activity of the PARG-encoding genes of the plants or plant cells; c.
  • Plants containing a stress tolerance-enhancing transgene encoding a plant-functional enzyme of the nicotinamide adenine dinucleotide salvage biosynthetic pathway including nicotinamidase, nicotinate phosphoribosyltransferase, nicotinic acid mononucleotide adenyltransferase, nicotinamide adenine dinucleotide synthetase or nicotinamide phosphoribosyltransferase.
  • Plants or plant varieties obtained by plant biotechnology methods such as genetic engineering which can also be treated according to the invention have a changed amount, quality and / or storability of the harvested product and / or altered characteristics of certain components of the harvested product, 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 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: a) plants such as cotton plants containing an altered form of cellulose synthase genes; b) plants such as cotton plants containing an altered form of rsw2 or rsw3 homologous nucleic acids; c) plants such as cotton plants having increased expression of sucrose phosphate synthase; d) plants such as cotton plants with increased expression of sucrose synthase; e) plants such as cotton plants in which the timing of the passage control of the Plasmodesmen is changed at the base of the fiber cell, z.
  • 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 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: a) plants, such as rape plants, that produce oil with a high oleic acid content; b) plants such as oilseed rape plants, which produce oil with a low linolenic acid content. c) plants such as rape plants that produce oil with a low saturated fatty acid content.
  • transgenic plants that can be treated according to the invention are plants having one or more genes encoding one or more toxins, and are the transgenic plants offered under the following tradenames: YIELD GARD® (for example, corn, cotton , Soybeans), KnockOut® (for example corn), BiteGard® (for example maize), BT-Xtra® (for example maize), StarLink® (for example corn), Bollgard® (cotton), Nucotn® (cotton), Nucotn 33B® (cotton), NatureGard® (for example corn), Protecta® and NewLeaf® (potato).
  • YIELD GARD® for example, corn, cotton , Soybeans
  • KnockOut® for example corn
  • BiteGard® for example maize
  • BT-Xtra® for example maize
  • StarLink® for example corn
  • Bollgard® cotton
  • Nucotn® cotton
  • Nucotn 33B® cotton
  • NatureGard® for example corn
  • Herbicide-tolerant crops to be mentioned are, 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® (sulfonylurea tolerance), for example corn.
  • Roundup Ready® glyphosate tolerance, for example corn, cotton, soybean
  • Liberty Link® phosphinotricin tolerance, for example rapeseed
  • IMI® imidazolinone tolerance
  • SCS® sulfonylurea tolerance
  • transgenic plants which can be treated according to the invention are plants which contain transformation events, or a combination of transformation events, and which are mentioned, for example, in the files of various national or regional authorities (see, for example) http: // gmoinfo .j rc. it / gmp_browse.aspx and http://www.agbios.com/dbase.php).
  • the listed plants can be treated particularly advantageously according to the invention with the compounds of general formula (I).
  • the preferred ranges given above for the active compounds or mixtures also apply to the treatment of these plants. Particularly emphasized is the plant treatment with the compounds or mixtures specifically mentioned in the present text.
  • the active compounds or compositions according to the invention can therefore be used to protect plants against the infestation by the named pests within a certain period of time after the treatment.
  • the period of time within which protection is afforded generally ranges from 1 to 28 days, preferably from 1 to 14 days, more preferably from 1 to 10 days, most preferably from 1 to 7 days after treatment of the plants with the active ingredients or up to 200 days after seed treatment.
  • triphenylphosphine 21.7 g (0.082 mol, 3 eq) of triphenylphosphine are dissolved in 70 ml of tetrahydrofuran and cooled to 0 ° C. by cooling with ice. Under argon, 25mL of a solution of 23.8g (2eq, 0.055mol) of diethyl azodicarboxylate (DEAD) in toluene are added slowly, the internal temperature does not exceed 20 ° C.
  • DEAD diethyl azodicarboxylate
  • XV-a-2 1.80 g (7.9 mmol) N- (4-Bromopyridin-2-yl) propanamide and 2.19 g (8.6 mmol) of bis (pinacolato) -diborane are dissolved in 50 mL of dry dioxane.
  • the mixture is then heated in the microwave at 150 ° C for 20 min (CEM Discover). Subsequently, the crude mixture is filtered through a cartridge with Celite and the volatile components are removed in vacuo.
  • the crude product is purified by chromatography on silica gel (cyclohexane / ethyl acetate) and there are 47.4 mg of 4- [5- (4-fluorophenyl) -1- (tetrahydro-2H-pyran-2-yl) -1H-pyrazol-4-yl ] pyridine (30%) and 41 mg of the cleaved product 4- [3- (4-fluorophenyl) -1H-pyrazol-4-yl] pyridine [IX-1] (35%) as a colorless oil.
  • [1-2] 50 mg (0.18 mmol) N- [4- (4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl) pyridin-2-yl] propanamide and 42 mg (0.13 mmol) 4-bromo-3- (4-fluoro-phenyl ) -l- (2-methoxyethyl) -1H-pyrazole are dissolved in 2.5 mL 1,4-dioxane.
  • the resulting suspension is filtered and the crude product is purified by preparative HPLC (XTerra 125x19 mm, 5 ⁇ , gradient: 0-1.5 min 80% water, 15% methanol, 5% aqueous 10% NH 4 HC0 3 -Lsg, 1.5-10.0 min linear gradient to 15% water, 80% methanol, 5% aqueous 10% NH 4 HC0 3 solution, 10.0-15.0 min 15% water, 80% methanol, 5% aqueous 10% NH 4 HCO 3 - Lsg) cleaned.
  • preparative HPLC XTerra 125x19 mm, 5 ⁇ , gradient: 0-1.5 min 80% water, 15% methanol, 5% aqueous 10% NH 4 HC0 3 -Lsg, 1.5-10.0 min linear gradient to 15% water, 80% methanol, 5% aqueous 10% NH 4 HC0 3 solution, 10.0-15.0 min 15% water, 80% methanol, 5% aqueous 10% NH 4 HCO 3 - Lsg

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Abstract

La présente invention concerne des phénylpyri(mi)dinylazoles représentés par les formules [I-a] et [I-b], dans lesquelles les symboles ont la signification qu'en donne la description. L'invention concerne également des sels de phénylpyri(mi)dinylazole dotés d'une action agrochimique, et leur utilisation, dans le cadre de la protection des végétaux et des matériaux, pour lutter contre des microorganismes indésirables, et pour réduire les mycotoxines dans les végétaux et les parties des végétaux. L'invention concerne enfin un procédé de fabrication de composés représentés par les formules [I-a] et [I-b].
EP10767974A 2009-10-09 2010-10-04 Phenylpyri(mi)dinylpyrazoles et leur utilisation comme fongicides Withdrawn EP2486031A2 (fr)

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CN102834387A (zh) 2012-12-19
US20130281455A1 (en) 2013-10-24
TW201127289A (en) 2011-08-16
EP2784071A1 (fr) 2014-10-01
IN2012DN02601A (fr) 2015-09-04
EP2784073A1 (fr) 2014-10-01
JP2013507334A (ja) 2013-03-04
CA2773205A1 (fr) 2011-04-14
CL2012000752A1 (es) 2012-10-05
AR078574A1 (es) 2011-11-16
EP2784072A1 (fr) 2014-10-01
EP2784070A1 (fr) 2014-10-01
KR20120101338A (ko) 2012-09-13
WO2011042389A2 (fr) 2011-04-14
US20110183978A1 (en) 2011-07-28
WO2011042389A3 (fr) 2012-08-16
BR112012007078A2 (pt) 2015-09-15
ECSP12011749A (es) 2012-10-30
RU2012111701A (ru) 2013-11-20
EP2308866A1 (fr) 2011-04-13
MX2012003600A (es) 2012-04-19

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