EP1628948A1 - Difluoromethylbenzanilides and use thereof for combating micro-organisms, intermediate products and use thereof - Google Patents

Difluoromethylbenzanilides and use thereof for combating micro-organisms, intermediate products and use thereof

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Publication number
EP1628948A1
EP1628948A1 EP04732289A EP04732289A EP1628948A1 EP 1628948 A1 EP1628948 A1 EP 1628948A1 EP 04732289 A EP04732289 A EP 04732289A EP 04732289 A EP04732289 A EP 04732289A EP 1628948 A1 EP1628948 A1 EP 1628948A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
formula
chlorine
cycloalkyl
halogen
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Withdrawn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
EP04732289A
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German (de)
French (fr)
Inventor
Ralf Dunkel
Hans-Ludwig Elbe
Jörg Nico GREUL
Benoit Hartmann
Ulrike Wachendorff-Neumann
Peter Dahmen
Karl-Heinz Kuck
Heiko Rieck
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Bayer CropScience AG
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Bayer CropScience AG
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Filing date
Publication date
Priority claimed from DE10325438A external-priority patent/DE10325438A1/en
Application filed by Bayer CropScience AG filed Critical Bayer CropScience AG
Publication of EP1628948A1 publication Critical patent/EP1628948A1/en
Withdrawn legal-status Critical Current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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/65—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/66—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/76—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by doubly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/77—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/68—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings containing halogen
    • C07C63/70—Monocarboxylic acids

Definitions

  • the present invention relates to new difluoromethylbenzanilides, several processes for their preparation and their use for controlling unwanted microorganisms.
  • EP-A 0 545 099 JP-A 2001-302605, JP-A 8-176112
  • EP-A 0 554099 already includes N- (4'-fluoro-l, l'-biphenyl-2-yl) -2- (trifluoromethyl) benzamide and N- (2-5ec-butylphenyl) -2- (trifluoromethyl) ) known benzamide.
  • the effectiveness of these substances is good, but in some cases, e.g. to be desired at low application rates.
  • Difluoromethylbenzanilides have so far not become known.
  • R 1 , R 2 , R 3 and R 4 independently of one another for hydrogen, fluorine, chlorine, methyl, iso-propyl or
  • R 5 is hydrogen, CC 8 -alkyl, -C-C 6 -alkylsulfmyl, CC 6 -alkylsulfonyl, C, -C 4 -alkoxy-C ⁇ - C 4 alkyl, C 3 -C 8 cycloalkyl; -C-C 6 -haloalkyl, - -haloalkylthio, CC 4 -haloalkyl -sulfinyl, C ⁇ -C 4 -haloalkylsulfonyl, halogen-C ⁇ -C 4 -alkoxy-C ⁇ -C -alkyl, C 3 -C 8 -halo-cycloalkyl with in each case 1 to 9 fluorine, chlorine and / or bromine atoms, formyl-C 3 -alkyl, (CC 3 -alkyl) carbonyl-C 3 -alkyl, (-CC 3 alkoxy) carbon
  • Halogencycloalkyl each with 1 to 9 fluorine, chlorine and / or bromine atoms; -COR 11 stands, R 7 and R 8 independently of one another for hydrogen, -CC 8 -alkyl, CC 4 -alkoxy -CC-C 4 alkyl, C 3 -C 8 - cycloalkyl; CC 8 -haloalkyl, halo -CC -alkoxy -CC-C 4 -alkyl, C 3 -C 8 -halogenocycloal yl each having 1 to 9 fluorine, chlorine and / or bromine atoms,
  • R 7 and R 8 together with the nitrogen atom to which they are attached also form a saturated or heterocycle which has 5 to 8 ring atoms and may be mono- or polysubstituted, identically or differently, by halogen or C r C 4 -alkyl, where the
  • Heterocycle 1 or 2 further, non-adjacent heteroatoms from the series oxygen,
  • R 9 and R 10 independently of one another for hydrogen, -CC 8 alkyl, C 3 -C 8 cycloalkyl; CC 8 halogen al yl, C 3 -C 3 halocycloalkyl each having 1 to 9 fluorine, chlorine and / or bromine atoms,
  • R 9 and R 10 together with the nitrogen atom to which they are attached, form a saturated heterocycle having 5 to 8 ring atoms, which is optionally mono- or polysubstituted, identically or differently, by halogen or -CC alkyl, the heterocycle 1 or can contain 2 further, non-adjacent heteroatoms from the series oxygen, sulfur or NR 12 ,
  • R 11 is hydrogen, CC 8 alkyl, - alkoxy, C r C 4 alkoxy-C 1 -C 4 alkyl, C 3 -C 8 cycloalkyl; C 1 -C 6 -haloalkyl, dC 6 -haloalkoxy, halogen-C 1 -C 8 -alkoxy-C 1 -C 8 -alkyl, C 3 -C 8 - halocycloalkyl, each with 1 to 9 fluorine, chlorine and or bromine atoms, R 12 represents hydrogen or Ci-Cg-alkyl,
  • Z stands for Z ⁇ Z 2 , Z 3 or Z 4 , wherein
  • Z 1 represents phenyl which is monosubstituted to pentas, identical or differently substituted
  • Z 2 is optionally monosubstituted or polysubstituted by identical or different substituents, cycloalkyl or bicycloalkyl
  • Z 3 represents unsubstituted C 2 -C 2 o alkyl or mono- or polysubstituted, identically or differently, by halogen and / or C 3 -C 6 cycloalkyl substituted - o-alkyl, where the cycloalkyl part in turn can optionally be substituted one or more times, identically or differently, by halogen and / or C r C 4 alkyl
  • Z 4 represents C 2 -C 20 alkenyl or C 2 -C 2 o-alkynyl which is optionally mono- or polysubstituted, identically or differently, by halogen and / or C 3 -C 6 -cycloalkyl, the cycloalkyl part in turn optionally single or can be substituted several times, identically or differently by halogen and / or C 1 -C 4 alkyl, or
  • R 1 , R 2 and R 3 independently represent hydrogen or fluorine and Z and R 4 together with the carbon atoms to which they are attached form an optionally substituted 5- or 6-membered carbocyclic or heterocyclic ring. It has furthermore been found that difluoromethylbenzanilides of the formula (I) are obtained by a) difluoromethylbenzoyl derivatives of the formula (II)
  • X 1 represents chlorine or hydroxy, with aniline derivatives of the formula (HI)
  • R, R 2 , R 3 , R 4 , R and Z have the meanings given above, optionally in the presence of a catalyst, optionally in the presence of a condensing agent, optionally in the presence of an acid binder and optionally in
  • R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given above, and X 2 represents chlorine, bromine, iodine or trifluoromethyl sulfonate, with boronic acid derivatives of the formula (V)
  • a 1 and A 2 each represent hydrogen or together represent tetramethylethylene, in the presence of a catalyst, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or c) difluoromethylbenzamide-boronic acid-D
  • R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given above, and
  • a 3 and A 4 each represent hydrogen or together represent tetramethylethylene, with phenyl derivatives of the formula (VII) X 3 - Z 1 (Q) in which Z 1 has the meanings given above and
  • X 3 represents chlorine, bromine, iodine or trifluoromethyl sulfonate, in the presence of a catalyst, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or d) halodifluoromethylbenzanilides of the formula (TV)
  • R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given above, and X 2 represents chlorine, bromine, iodine or trifluoromethyl sulfonate, with phenyl derivatives of the formula (VII)
  • X 3 represents chlorine, bromine, iodine or trifluoromethyl sulfonate, in the presence of a palladium or nickel catalyst and in the presence of
  • R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given above and
  • X 4 stands for C 2 -C 2 o-alkenyl or C 2 -C 2 o-alkynyl which is optionally mono- or polysubstituted, identically or differently, by halogen and / or C 3 -C 6 -cycloalkyl, the cycloalkyl part in turn being optionally substituted by Halogen and / or C r C 4 alkyl may be substituted, optionally hydrogenated in the presence of a diluent and optionally in the presence of a catalyst, or f) hydroxyalkyl-difluoromethylbenzanilides of the formula (VIII)
  • R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given above and X 5 for C 2 -C 2 which is optionally monosubstituted or polysubstituted, identically or differently, by halogen and / or C 3 -C 6 -cycloalkyl stands for o-hydroxyalkyl, where the cycloalkyl part in turn can optionally be substituted by halogen and / or C 1 -C 4 alkyl, optionally dehydrated in the presence of a diluent and optionally in the presence of an acid, or g) halodifluoromethylbenzanilides of the formula (TV)
  • R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given above, and
  • X 2 represents chlorine, bromine, iodine or trifluoromethyl sulfonate, with an alkyne of the formula (IX) HC ⁇ — A 5 (IX), in which
  • a 5 is in each case optionally mono- or polysubstituted, identically or differently, by halogen and / or C 3 -C 6 -cycloalkyl-substituted C 2 -C 8 -alkyl, the cycloalkyl part in turn optionally being substituted by halogen and or C r C 4 -alkyl or an alkene of the formula (X)
  • a 6 , A 7 and A 8 each independently represent hydrogen or optionally mono- or polysubstituted, identically or differently, alkyl substituted by halogen and / or C 3 -C 6 -cycloalkyl, the cycloalkyl part in turn optionally being substituted by halogen and / or C ⁇ - C - alkyl can be substituted and the total number of
  • R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given above and
  • a 9 represents hydrogen or optionally mono- or polysubstituted, identically or differently, C 1 -C 8 -alkyl substituted by halogen and / or C 3 -Cycloalk l, where the cycloalkyl part in turn may optionally be substituted by halogen and or CC-alkyl, with a phosphorus compound of the general formula (Xu)
  • R 6 , R 7 , R 8 , R 9 and R 10 have the meanings given above and X 6 represents chlorine, bromine or iodine, in the presence of a base and in the presence of a diluent.
  • the difluoromethylbenzanilides of the formula (I) according to the invention show a substantially better fungicidal activity than the constitutionally most similar, known active substances of the same direction of action.
  • the compounds according to the invention can optionally be in the form of mixtures of various possible isomeric forms, in particular stereoisomers, such as, for. B. E and Z, threo and erythro, and optical isomers, but optionally also of tautomers are present. Both the E and the Z isomers, as well as the threo and erythro and optical isomers, any mixtures of these isomers and the possible tautomeric forms are claimed.
  • the difluoromethylbenzanilides according to the invention are generally defined by the formula (I).
  • Preferred radical definitions of the formulas mentioned above and below are given below. These definitions apply equally to the end products of the formula (I) and to all intermediates.
  • R 1 , R 2 , R 3 and R 4 independently of one another preferably represent hydrogen, fluorine, chlorine or methyl.
  • R 1 particularly preferably represents hydrogen or fluorine.
  • R 1 very particularly preferably represents hydrogen.
  • R 1 also very particularly preferably represents fluorine.
  • R 2 particularly preferably represents hydrogen.
  • R 3 particularly preferably represents hydrogen, fluorine, chlorine or methylthio.
  • R 3 very particularly preferably represents hydrogen.
  • R 3 also very particularly preferably represents fluorine.
  • R 4 particularly preferably represents hydrogen, methyl or isopropyl.
  • R 4 very particularly preferably represents hydrogen.
  • R 4 also very particularly preferably represents methyl.
  • R 1 , R 2 , R 3 and R 4 very particularly preferably simultaneously represent hydrogen.
  • R 5 preferably represents hydrogen; -C 6 -alkyl, CC 4 -alkylsulfinyl, dC 4 -alkylsulfonyl, d- C3-alkoxy-C 3 -C 3 -alkyl, C 3 -C 6 -cycloalkyl; C r C 4 haloalkyl, dC 4 haloalkylthio, haloalkylsulfinyl dC, CC 4 -haloalkylsulfonyl, halo-C ⁇ -C3-alkoxy-C C 3 alkyl, C 3 -C ö halocycloalkyl having in each case 1 to 9 Fluorine, chlorine and / or bromine atoms, formyl-CC 3 -alkyl, (dC 3 -
  • R 5 particularly preferably represents hydrogen, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, pentyl or hexyl, methylsulfinyl, ethylsulfinyl, n- or iso-propylsulfinyl, n-, iso-, sec- or tert-butylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or iso-propylsulfonyl, n-, iso-, sec- or tert-butylsulfonyl, methoxymethyl, methoxyethyl, ethoxymethyl,
  • R 5 very particularly preferably represents hydrogen; Methyl, methoxymethyl, -CH 2 -CHO, -CH 2 CH 2 -CHO, -CH 2 -CO-CH 3 , -CH 2 -CO-CH 2 CH 3 , -CH 2 -CO-CH (CH 3 ) 2 or -COR 6 .
  • R 6 preferably represents hydrogen, CC 6 alkyl, CC 4 alkoxy, CC 3 alkoxy-dC 3 alkyl, C 3 -
  • R 6 particularly preferably represents hydrogen, methyl, ethyl, n- or iso-propyl, tert-butyl, methoxy, ethoxy, iso-propoxy, tert-butoxy, cyclopropyl; Trifluoromethyl, trifluoromethoxy,
  • -COR 11 R 6 very particularly preferably represents hydrogen, -COCH 3 , -CHO, -COCH 2 OCH 3 ,
  • R 7 and R 8 independently of one another preferably represent hydrogen, CC 6 -alkyl, dC 3 -alkoxy-C r C 3 -alkyl, C 3 -C 6 -cycloalkyl; C, -C 4 haloalkyl, halo -CC 3 alkoxy-C r C 3 alkyl, C 3 -C 6 -
  • Halogencycloalkyl each with 1 to 9 fluorine, chlorine and / or bromine atoms.
  • R 7 and R 8 together with the nitrogen atom to which they are attached, preferably form a saturated heterocycle having 5 to 8 ring atoms, which is optionally monosubstituted to tetrasubstituted, identically or differently, by halogen or CQ-alkyl, the heterocycle 1 or can contain 2 further, non-adjacent heteroatoms from the series oxygen, sulfur or NR 12 .
  • R 7 and R 8 independently of one another particularly preferably represent hydrogen, methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, cyclopropyl, cyclopentyl, cyclohexyl ; Trifluoromethyl, trichloromethyl, trifluoroethyl, trifluoromethoxymethyl.
  • R 7 and R 8 together with the nitrogen atom to which they are attached, particularly preferably form one optionally up to four times, identical or different by fluorine,
  • R 9 and R 10 independently of one another are preferably hydrogen, -CC 6 -alkyl, C 3 -C 6 -cycloal- yl; CC 4 haloalkyl, C 3 -C 6 halocycloalkyl each having 1 to 9 fluorine, chlorine and / or bromine atoms.
  • R 9 and R 10 together with the nitrogen atom to which they are attached, preferably form one optionally one or more times, identically or differently, by halogen or C r
  • R 9 and R 10 independently of one another particularly preferably represent hydrogen, methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl, methoxymethyl, methoxyethyl, ethoxymethyl,
  • R 9 and R 10 together with the nitrogen atom to which they are attached, particularly preferably form a saturated heterocycle from the series morpholine which may be mono- to tetrasubstituted, identically or differently, by fluorine, chlorine, bromine or methyl, Thiomo holin or piperazine, where the piperazine on the second nitrogen atom can be substituted by R 12 .
  • R 11 preferably represents hydrogen, CC 6 -alkyl, C r C 4 -alkoxy, C, -C 3 -alkoxy-C r C 3 -alkyl, C 3 - C 6 -cycloalkyl; CC 4 haloalkyl, CC 4 -haloalkoxy, halo-C C 3 alkoxy-C r C 3 - alkyl, C 3 -C 6 -halocycloalkyl having in each case 1 to 9 fluorine, chlorine and / or bromine atoms.
  • R ⁇ particularly preferably represents hydrogen, methyl, ethyl, n- or isopropyl, tert-butyl,
  • R 12 preferably represents hydrogen or CC 4 alkyl.
  • R 12 particularly preferably represents hydrogen, methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl.
  • Z preferably represents Z 1 .
  • Z 1 preferably represents phenyl which is monosubstituted to pentas, identical or differently substituted, the substituents being selected from the list W 1 .
  • Z 1 particularly preferably represents monosubstituted phenyl, where the substituents from
  • List W 1 are selected.
  • Z 1 also particularly preferably represents phenyl which is substituted twice, identically or differently, the substituents being selected from the list W 1 .
  • Z 1 also particularly preferably represents triple, identical or differently substituted phenyl, the substituents being selected from the list W 1 .
  • Z 1 very particularly preferably represents phenyl which is monosubstituted in the 4-position, the
  • Substituents are selected from the list W 1 .
  • Z 1 very particularly preferably represents phenyl which is substituted twice, identically or differently in the 3,4-position, the substituents being selected from the list W 1 .
  • Z 1 very particularly preferably represents phenyl which is substituted twice, identically or differently in the 2,4-position, the substituents being selected from the list W 1 .
  • Z 1 very particularly preferably represents phenyl which is substituted twice, identically or differently in the 3,5-position, the substituents being selected from the list W 1 .
  • Z 1 very particularly preferably represents phenyl which is substituted three times, identically or differently in the 2,4,6-position, the substituents being selected from the list W 1 .
  • W 1 stands for halogen, cyano, nitro, amino, hydroxy, formyl, carboxyl, carbamoyl, thiocarbamoyl; in each case straight-chain or branched alkyl, hydroxyalkyl, oxoalkyl, alkoxy,
  • Haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms; each straight-chain or branched haloalkenyl or haloalkenyloxy each having 2 to 6 carbon atoms and 1 to 11 identical or different halogen atoms; each straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, arylalkylaminocarbonyl, dial ylaminocarbonyloxy with 1 to 6 carbon atoms in the respective hydrocarbon chains, alkenylcarbonyl or alkynylcarbonyl, with 2 to 6 carbon atoms hydrocarbon chains;
  • Q 1 represents hydrogen, hydroxyl, alkyl having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms or cycloalkyl having 1 to 6 carbon atoms and Q 2 is hydroxyl, amino, methylamino, phenyl, benzyl or for alkyl or alkoxy with 1 to 4 carbon atoms, each optionally substituted by halogen, cyano, hydroxy, alkoxy, alkylthio, alkylamino, dialkylamino or phenyl, or for alkenyloxy or alkynyloxy each with 2 to 4 carbon atoms, and in each case optionally in the ring part simply to phenyl, phenoxy, phenyllthio, benzoyl, benzoylethenyl, cinnamoyl, heterocyclyl or phenylalkyl, phenylalkyloxy, phenylalkylthi
  • Q 1 represents hydrogen, methyl, ethyl, trifluoromethyl or cyclopropyl
  • Q 2 represents hydroxy, methoxy, ethoxy, propoxy or isopropoxy.
  • Z also preferably represents Z 2 .
  • Z 2 preferably represents optionally up to four times, identical or different, by C 1 -C 4 -
  • Z 2 particularly preferably represents cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, bicyclo [2.2. l] heptyl or bicyclo [2.2.2] octyl.
  • Z also preferably represents Z 3 .
  • Z 3 preferably stands for unsubstituted C 2 -C 20 alkyl or for mono- or polysubstituted, identically or differently, by fluorine, chlorine, bromine, iodine and / or C 3 -C 6 cycloalkyl-substituted -CC 20 alkyl, where the cycloalkyl part, in turn, may optionally be substituted up to four times, identically or differently, by fluorine, chlorine, bromine, iodine, CC 4 alkyl and / or CC 4 haloalkyl.
  • Z 3 particularly preferably represents unsubstituted C 2 -C 20 -alkyl.
  • Z 3 also particularly preferably represents d-do-alkyl substituted by chlorine, cyclopropyl, dichlorocyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • Z also preferably represents Z 4 .
  • Z 4 preferably represents C 2 -C 20 alkenyl or C 2 -C 20 alkynyl which is optionally substituted once or several times, identically or differently, by fluorine, chlorine, bromine, iodine and / or C 3 -C 6 cycloalkyl, the cycloalkyl part in turn optionally up to four times, identical or different by fluorine, chlorine, bromine, iodine, CC 4 alkyl and / or C
  • C 4 haloalkyl may be substituted.
  • Z 4 particularly preferably represents C 2 -C 20 alkenyl or C 2 -C 0 alkynyl.
  • Z and R 4 are also preferably, together with the carbon atoms to which they are attached, an optionally mono- to tetrasubstituted, identical or differently substituted 5- or
  • Z and R 4 are also particularly preferably, together with the carbon atoms to which they are attached, an optionally mono-, di- or trisubstituted by methyl-substituted 5- or 6-membered carbocyclic ring.
  • Compounds of the formula (Ic) are also preferred
  • R 5 "1 preferably represents CC 6 -alkyl, dC 4 -alkylsulfinyl, dC 4 -alkylsulfonyl, C r C 3 -alkoxy-dC 3 -alkyl, C 3 -C 6 -cycloalkyl; C ⁇ -C 4 -haloalkyl, CC 4 -haloalkylthio, CC 4 - haloalkylsulfmyl, CC 4 -haloalkylsulfonyl, halo-dd-alkoxy-Crd-alkyl, C 3 - C 6 -halo-cycloalkyl, each with 1 to 9 fluorine, chlorine and / or bromine atoms, formyl-d- d-alkyl, (-C-C 3 alkyl) carbonyl-dC 3 -alkyl, (CC 3 -alkoxy) carbonyl-C r C 3 -
  • R 5 "1 particularly preferably represents methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl, pentyl or hexyl, methylsulfmyl, ethylsulfmyl, n- or iso-propylsulfmyl, n-, iso-, sec- or tert-butylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or iso-propylsulfonyl, n-, iso-, sec- or tert-butylsulfonyl, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, cyclopropyl, cyclopentyl, cyclohexyl, trifluoromethyl, Trichloromethyl, trifluoroethyl,
  • R 5 "1 very particularly preferably represents methyl, methoxymethyl, -CH 2 -CHO, -CH 2 CH 2 -CHO, -CH 2 -CO-CH 3 , -CH 2 -CO-CH 2 CH 3 , -CH 2 -CO-CH (CH 3 ) 2 or -COR 6 .
  • Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl can also be used in
  • C r C 20 alkyl encompasses the largest range defined here for an alkyl radical. Specifically, this definition includes the meanings methyl, ethyl, n-, iso-propyl, n-, iso-, sec-, tert-butyl, and all isomeric pentyls, hexyls, heptyls, octyls, nonyls, decyls, undecyls and dodecyls , Tridecyle, Tetradecyle, Pentadecyle, Hexadecyle, Heptadecyle, Octadecyle, Nonadecyle and Eicosyle.
  • alkenyl encompasses the largest range defined here for an alkenyl radical. Specifically, this definition includes the meanings ethenyl, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, l -Methyl-2-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, and in each case all isomeric pentenyls, hexenyls, heptenyls, octenyls, nonenyls, decenyls, undecenyls, dodecenyls, tridecenyls, tetradecenyls, pentadecenyls, hexadecenyls, heptadecenyls , Nonadecenyl,
  • Preferred meanings are ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-pentenyl, 4-pentenyl , 1-methyl-1-butenyl, 1,2-dimethyl-1-propenyl, 1-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1,3-dimethyl-1-butenyl, 1-methyl-1 -hexenyl, 1,3,3 -trimethyl-1-butenyl.
  • C 2 -C 20 alkynyl encompasses the largest range defined here for an alkynyl radical. Specifically, this definition includes the meanings ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, l-methyl-2-propynyl, as well as all isomeric pentynyls, hexinyls, heptinyls, octynyls, noninyls , Decinyle, Undecinyle, Dodecinyle, Tridecinyle, Tetradecinyle, Pentadecinyle, Hexadecinyle, Heptadecinyle, Octadecinyle, Nonadecinyle and Eicosinyle.
  • Preferred meanings are ethynyl, 1-propynyl, 1-butynyl, 3-butynyl, l-methyl-2-propynyl, 1-pentynyl, 4-pentynyl, 1-hexynyl, 5-hexynyl, 3,3-dimethyl-l -butinyl, 4,4-dimethyl-1-pentynyl, 4,4-dimethyl-2-pentynyl, 1,4-dimethyl-2-pentynyl.
  • Optionally substituted radicals can be mono- or polysubstituted, and in the case of multiple substitutions the substituents can be the same or different.
  • Residues substituted by halogen such as haloalkyl, are halogenated once or more than once. In the case of multiple halogenation, the halogen atoms can be the same or different.
  • Halogen stands for fluorine, chlorine, bromine and iodine, in particular for fluorine, chlorine and bromine.
  • Formula (II) provides a general definition of the difluoromethylbenzoyl derivatives required as starting materials for carrying out process (a) according to the invention.
  • X 1 preferably represents chlorine or hydroxy.
  • Formula (HI) provides a general definition of the aniline derivatives which are further required as starting materials for carrying out process (a) according to the invention.
  • R 1 , R 2 , R 3 , R 4 , R 5 and Z have preferred, particularly preferably or very particularly preferably, those meanings which have already been associated with the description of the compounds of the formula (I) according to the invention as preferred, particularly preferred or very particularly preferred for these radicals.
  • Halogen-difluoromethylbenzanilides are generally defined by the formula (TV).
  • R 1 , R 2 , R 3 , R 4 and R 5 have preferred, particularly preferably or very particularly preferably those meanings which have already been preferred in connection with the description of the compounds of the formula (I) according to the invention , particularly preferred or very particularly preferred for these radicals.
  • X 2 stands for
  • halodifluoromethylbenzanilides of the formula (TV) are not yet known. As new chemical compounds, they are also the subject of the present application. They are obtained by k) difluoromethylbenzoyl derivatives of the formula (H)
  • R, R, R, R, R and X 2 have the meanings given above, if appropriate in the presence of a catalyst, if appropriate in the presence of a condensing agent, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent.
  • Formula (XVI) provides a general definition of the halogen anilines which are further required as starting materials for carrying out process (k) according to the invention.
  • R 1 , R 2 , R 3 , R 4 , R 5 and X 2 have preferred, particularly preferably or very particularly preferably those meanings which have already occurred in connection with the description of the compounds of the formula (I ), or the precursors of the formula (HI) were given as preferred, particularly preferred or very particularly preferred for these radicals.
  • haloanilines of the formula (XVI) are known synthetic chemicals or can be obtained by known processes.
  • R 5 is not hydrogen
  • the radical R 5 can be introduced at the level of the compounds of the formula (XVI) by customary derivatization methods. It is also possible first to prepare compounds of the formula (TV) in which R 5 is hydrogen and then to derivatize the products obtained by customary methods (cf. process (i) according to the invention).
  • Formula (V) provides a general definition of the boronic acid derivatives which are further required as starting materials for carrying out process (b) according to the invention.
  • Z 1 has preferred, particularly preferred or very particularly preferred those meanings which have already been given as preferred, particularly preferred or very particularly preferred for Z 1 in connection with the description of the compounds of the formula (I) according to the invention were.
  • a 1 and A 2 each represent hydrogen or together represent tetramethylethylene.
  • the boronic acid derivatives of the formula (V) are known and / or can be prepared by known processes (cf., for example, WO 01/90084 and US 5,633,218).
  • Difluoromethylbenzamide boronic acid derivatives are generally defined by the formula (VI).
  • R 1, R 2, R 3, R 4 and R 5 have preferred, particularly preferred and very particularly preferably have those meanings already mentioned in connection with the description of ER- inventive compounds of formula (I) as preferred, particularly preferred or very particularly preferred for these radicals.
  • a 3 and A 4 each represent hydrogen or together represent tetramethylethylene.
  • the difluoromethylbenzamide-boronic acid derivatives of the formula (VI) are not yet known. They are new chemical compounds and are also the subject of the present application. They are obtained by 1) difluoromethylbenzoyl derivatives of the formula (H)
  • R 1 , R 2 , R 3 , R 4 , R 5 , A 3 and A 4 have the meanings given above, if appropriate in the presence of a catalyst, if appropriate in the presence of a condensing agent, if appropriate in the presence of an acid binder and if appropriate in
  • Formula (XV ⁇ ) generally defines the aniline boronic acid derivatives which are further required as starting materials for carrying out process (1) according to the invention.
  • R 1 , R 2 , R 3 , R 4 and R 5 have preferred, particularly preferably or very particularly preferably, those meanings which have already occurred in connection with the description of the compounds of the formula (I) according to the invention as preferred, particularly preferred or very particularly preferred for these radicals.
  • a 3 and A 4 each represent hydrogen or together represent tetramethylethylene.
  • aniline boronic acid derivatives of the formula (XVII) are known synthetic chemicals or can be obtained by known processes.
  • the radical R 5 can be introduced at the level of the compounds of the formula (XVH) by customary derivatization methods. It is also possible first to prepare compounds of the formula (VI) in which R 5 is hydrogen and then to derivatize the products obtained by customary methods (cf. process (i) according to the invention).
  • Formula (VII) provides a general definition of the phenyl derivatives which are furthermore required as starting materials for carrying out process (c) according to the invention.
  • Z 1 has preferred, particularly preferred or very particularly preferred those meanings which have already been given as preferred, particularly preferred or very particularly preferred for Z 1 in connection with the description of the compounds of the formula (I) according to the invention were.
  • X 3 stands for chlorine, bromine, iodine or trifluoromethyl sulfonate.
  • VTT The phenyl derivatives of the formula (VTT) are known synthetic chemicals.
  • the 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bis-l, 3,2-dioxaborolane required to carry out process (d) according to the invention is commercially available chemical for synthesis.
  • Formula (Ia) provides a general definition of the difluoromethylbenzanilides required as starting materials for carrying out process (e) according to the invention.
  • R 1 , R 2 , R 3 , R 4 and R 5 have preferred, particularly preferably or very particularly preferably those meanings which have already been preferred in connection with the description of the compounds of the formula (I) according to the invention , particularly preferred or very particularly preferred for these radicals.
  • the compounds of the formula (Ia) are compounds according to the invention and can be prepared by processes (a), (f), (g) or (h). Method (f)
  • Formula (VHI) provides a general definition of the hydroxyalkyl difluoromethylbenzanilides required as starting materials for carrying out process (f) according to the invention.
  • R 1, R 2, R 3, R 4 and R 5 have preferred, particularly preferred and very particularly preferably have those meanings already mentioned in connection with the description of ER- inventive compounds of formula (I) as preferred, particularly preferred or very particularly preferred for these radicals.
  • X 5 preferably represents C 2 -C 2 -hydroxyalkyl which is optionally monosubstituted to tetrasubstituted, identically or differently, by chlorine, fluorine, bromine and / or dQ-cycloalkyl, the cycloalkyl part in turn optionally being halogen and / or dC 4 -alkyl can be substituted.
  • X 5 particularly preferably represents optionally up to four times, identically or differently, substituted by fluorine, cyclopropyl, difluorocyclopropyl, cyclobutyl, cyclopentyl and / or cyclohexyl, in each case straight-chain or branched, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl,
  • VHI hydroxyalkyl difluoromethylbenzanilides
  • hydroxyalkyl difluoromethylbenzanilides of the formula (VHI) are obtained by m) difluoromethylbenzoyl derivatives of the formula (H) in which X 1 represents halogen or hydroxy, with hydroxyalkylaniline derivatives of the formula (XVHI)
  • R 1 , R 2 , R 3 , R 4 , R 5 and X 5 have the meanings given above, if appropriate in the presence of a catalyst, if appropriate in the presence of a condensing agent, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent.
  • Formula (XVHI) provides a general definition of the hydroxyalkylaniline derivatives which are further required as starting materials for carrying out process (1) according to the invention.
  • R 1 , R 2 , R 3 , R 4 , R 5 and X 5 have preferred, particularly preferably or very particularly preferably those meanings which have already been connected with the description of the compounds of the formulas (I ) or (VHT) as preferred, particularly preferred or very particularly preferred for these radicals.
  • the hydroxyalkylaniline derivatives of the formula (XVHI) are known and / or can be obtained by known methods (cf., for example, US Pat. No. 3,917,592 or EP-A 0 824099).
  • R 5 is not hydrogen
  • the radical R 5 can be introduced at the level of the compounds of the formula (XVIII) by customary derivatization methods. It is also possible to first prepare compounds of the formula (VIH) in which R 5 represents hydrogen and then to derivatize the products obtained by customary methods [cf. the inventive method (i)].
  • Formula (IX) provides a general definition of the alkynes further required as starting materials for carrying out process (g) according to the invention.
  • cycloalkyl moiety for its part is optionally substituted by halogen and / or CC - substituted alkyl can be.
  • alkynes of the formula (VI) are known synthetic chemicals.
  • Formula (X) provides a general definition of the alkenes which are alternatively required as starting materials for carrying out process (g) according to the invention.
  • a 6 , A 7 and A 8 independently of one another preferably each represent hydrogen or, if appropriate, up to four times, identically or differently, by fluorine, chlorine, bromine and / or C 3 -C 6 -
  • Cycloalkyl substituted alkyl the cycloalkyl part in turn optionally being replaced by
  • Halogen and / or C] -C alkyl may be substituted and the total number of
  • Carbon atoms of the open-chain part of the molecule does not exceed the number 12.
  • a 6 , A 7 and A 8 independently of one another particularly preferably each represent hydrogen or, if appropriate, one to four times, identically or differently, by fluorine, cyclopropyl,
  • Difluorocyclopropyl, cyclobutyl, cyclopentyl and / or cyclohexyl substituted, in each case straight-chain or branched, ethyl, propyl, butyl, pentyl, hexyl, heptyl or acrylic, each linked at any desired position, the total number of carbon atoms in the open-chain part of the molecule not exceeding 12.
  • the alkenes of the formula (VH) are known synthetic chemicals.
  • Formula (XI) provides a general definition of the ketones required as starting materials for carrying out process (h) according to the invention.
  • R 1 , R 2 , R 3 , R 4 and R 5 have preferred, particularly preferably or very particularly preferably, those meanings which have already been preferred in connection with the description of the compounds of the formula (I) according to the invention, were particularly preferred or very particularly preferred for these radicals.
  • a 9 preferably represents optionally mono- to tetrasubstituted by identical or different fluorine, chlorine, bromine and or C 3 -C 6 cycloalkyl-substituted C 2 -C ⁇ 0 - alkyl, where the cycloalkyl moiety for its part is optionally substituted by halogen and / or C ⁇ -C 4 alkyl may be substituted.
  • a 9 particularly preferably represents optionally up to four times, identical or different from fluorine, cyclopropyl, difluorocyclopropyl, cyclobutyl, cyclopentyl and / or cyclohexyl Substituted, straight-chain or branched, in each case linked ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl.
  • ketones of the formula (VHI) are not yet known. As new chemical compounds, they are also the subject of the present application. They are obtained by n) difluoromethylbenzoyl derivatives of the formula (H)
  • Formula (XIX) provides a general definition of the ketoanilines which are further required as starting materials for carrying out process (s) according to the invention.
  • R 1, R 2, R 3, R 4, R 5 and A are 9 preferred, particularly preferred and very particularly preferred meanings, the gene already in connection with the description of the invention of formulas Verbindun- (I) or (XI) were given as preferred, particularly preferred or very particularly preferred for these radicals.
  • ketoanilines of the formula (XIX) are known (cf. J. Am. Chem. Soc. 1978, 100, 4842-4857 or US 4,032,573) and / or can be obtained by known methods.
  • R 5 is not hydrogen
  • the radical R 5 can be introduced at the level of the compounds of the formula (XXII) by customary derivatization methods. It is also possible first to prepare compounds of the formula (VIII) in which R 5 is hydrogen and then to derivatize the products obtained by customary methods (cf. process (i) according to the invention).
  • Formula (XII) provides a general definition of the phosphorus compounds which are further required as starting materials for carrying out process (h) according to the invention.
  • a 10 preferably represents optionally mono- to tetrasubstituted by identical or different substituents from chlorine, fluorine, bromine and / or C 3 -C 6 cycloalkyl-substituted C 2 -C ⁇ 0 alkyl, where the cycloalkyl moiety for its part may be substituted by halogen and / or C Q-alkyl can be substituted.
  • a 10 particularly preferably represents optionally up to four times, identical or different, substituted by fluorine, cyclopropyl, difluorocyclopropyl, cyclobutyl, cyclopentyl and / or cyclohexyl, in each case straight-chain or branched, ethyl, propyl, butyl, pentyl, hexyl, linked at any point, Heptyl or octyl.
  • the phosphorus compounds of the formula (XU) are known and / or can be prepared by known processes (cf. Justus Liebigs Ann. Chem. 1953, 580, 44-57 or Pure Appl. Chem. 1964, 9, 307-335).
  • Formula (Ib) provides a general definition of the difluoromethylbenzanilides required as starting materials for carrying out process (i) according to the invention.
  • R 1 , R 2 , R 3 , R 4 and Z have preferred, particularly preferably or very particularly preferably, those meanings which have already been preferred in connection with the description of the compounds of the formula (I) according to the invention, were particularly preferred or very particularly preferred for these radicals.
  • the compounds of the formula (Ib) are compounds according to the invention and can be prepared by processes (a) to (h).
  • Formula (XTTT) provides a general definition of the halides required as starting materials for carrying out process (i) according to the invention.
  • R 5 ′′ 1 is preferably, particularly preferably or very particularly preferably for those meanings which are already preferred, particularly preferred or very particularly preferred in connection with the description of the compounds of the formula (Ig) these residues have been indicated
  • X 6 represents chlorine, bromine or iodine.
  • Suitable diluents for carrying out processes (a), (k), (1), (m) and (n) are all inert organic solvents.
  • These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or
  • Processes (a), (k), (1), (m) and (n) according to the invention are optionally carried out in the presence of a suitable acid acceptor.
  • a suitable acid acceptor All conventional inorganic or organic bases are suitable as such. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, lithium diisopropylamide, narrium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide , Potassium hydroxide, sodium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethyl-benzylamine, pyridine, N-methylpiperidine
  • Processes (a), (k), (1), (m) and (n) according to the invention are optionally carried out in the presence of a suitable condensing agent.
  • a suitable condensing agent all condensation agents which can usually be used for such amidation reactions are suitable.
  • acid halide formers such as phosgene, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride or thionyl chloride
  • Anhydride formers such as ethyl chloroformate, methyl chloroformate, isopropyl chloroformate, isobutyl chloroformate or methanesulfonyl chloride
  • Carbodiimides such as N, N'-dicyclohexylcarbodiimide (DCC) or other customary condensing agents, such as phosphorus pentoxide, polyphosphoric acid, N, N'-carbonyldiimidazole, 2-eth
  • Processes (a), (k), (1), (m) and (n) according to the invention are optionally carried out in the presence of a catalyst.
  • a catalyst examples include 4-dimethylaminopyridine, 1-hydroxybenzotriazole or dimethylformamide.
  • reaction temperatures can be varied within a substantial range when carrying out processes (a), (k), (1), (m) and (n). In general, temperatures from 0 ° C to 150 ° C, preferably at temperatures from 0 ° C to 80 ° C.
  • Formula (TT) is generally used per mole of the difluoromethylbenzoyl derivative of the formula (TT)
  • ketoaniline of the formula 0.8 to 15 mol, preferably 0.8 to 8 mol, of ketoaniline of the formula are generally employed per mole of the difluoromethylbenzoyl derivative of the formula (TT) (XVI) a.
  • Suitable diluents for carrying out processes (b), (c) and (d) are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, e.g. Petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; Ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Nitriles such as acetonitrile, propionitrile, n- or iso-butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-
  • reaction temperatures can be varied within a substantial range when carrying out processes (b), (c) and (d) according to the invention. In general, temperatures from 0 ° C to 180 ° C, preferably at temperatures from 20 ° C to 150 ° C.
  • the processes (b), (c) and (d) according to the invention are optionally carried out in the presence of a suitable acid acceptor.
  • a suitable acid acceptor All conventional inorganic or organic bases are suitable as such. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, fluorides, phosphates, carbonates or hydrogen carbonates, such as sodium hydride, sodium amide, lithium diisopropyl amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide , Sodium acetate, sodium phosphate, potassium phosphate, potassium fluoride, cesium fluoride, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or cesium carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethyl
  • a catalyst such as, for example, a palladium salt or complex.
  • a catalyst such as, for example, a palladium salt or complex.
  • Palladium chloride, palladium acetate, tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride or (l, l'-bis (diphenylphosphino) ferrocene palladium ( ⁇ ) chloride) are preferably suitable for this purpose.
  • a palladium complex can also be generated in the reaction mixture if a palladium salt and a complex ligand, e.g. Triethylphosphane, tri-tert-butylphosphine, tricyclohexylphosphine, 2- (dicyclohexylphosphine) biphenyl, 2- (di-tert-butylphosphine) biphenyl, 2- (dicyclohexylphosphine) -2 '- (N, N-dimethylamino) -biphenyl, triphenylphosphine, tris (o-tolyl) phosphine, sodium 3- (diphenylphosphino) benzenesulfonate, tris-2- (methoxyphenyl) phosphine, 2,2'-bis (diphenylphosphine) -l, l ' -bmaphthyl, 1,4-bis (diphenylpho
  • 0.8 to 15 mol, preferably 0.8 to 8 mol, of phenyl derivative are generally employed per mole of the halodifluoromethylbenzanilide of the formula (IV) of the formula (VH) and 0.8 to 15 mol, preferably 0.8 to 8 mol of 4,4,4 ', 4 l , 5,5,5', 5'-octamethyl-2,2'-bis- l, 3,2-dioxaborolane.
  • Suitable diluents for carrying out process (e) according to the invention are all inert organic solvents.
  • aliphatic or alicyclic hydrocarbons such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane or decalin; Ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tefrahydrofuran, 1,2-dimethoxyethane or 1,2-diethoxyethane; Alcohols, such as methanol, ethanol, n- or iso-propanol, n-, iso-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.
  • aliphatic or alicyclic hydrocarbons such
  • the process (s) according to the invention is carried out in the presence of a catalyst.
  • All catalysts which are usually used for hydrogenations are suitable as such. Examples include: Raney nickel, palladium or platinum, optionally on a carrier material, such as activated carbon.
  • the hydrogenation in process (e) according to the invention can also be carried out in the presence of triethylsilane instead of in the presence of hydrogen in combination with a catalyst.
  • reaction temperatures can be varied within a substantial range when carrying out process (e) according to the invention. In general, temperatures from 0 ° C to 150 ° C, preferably at temperatures from 20 ° C to 100 ° C.
  • Process (e) according to the invention is carried out under a hydrogen pressure between 0.5 and 200 bar, preferably between 2 and 50 bar, particularly preferably between 3 and 10 bar.
  • Suitable diluents for carrying out process (f) according to the invention are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Ketones such as ace
  • Process (f) according to the invention is optionally carried out in the presence of an acid.
  • All inorganic and organic protonic and Lewis acids, as well as all polymeric acids, are suitable as such. These include, for example, hydrogen chloride, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, toluenesulfonic acid, boron trifluoride (also as etherate), boron tribromide, aluminum trichloride, titanium tetrachloride, tetrabutyl orthide chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride,
  • reaction temperatures can be varied within a substantial range when carrying out process (f) according to the invention. In general, temperatures from 0 ° C to 150 ° C, preferably at temperatures from 0 ° C to 100 ° C.
  • Processes (f) and (e) according to the invention can also be carried out in a tandem reaction (“one-pot reaction”).
  • a compound of the formula (VHI) is optionally in the presence of a diluent (suitable solvents as for process (f)), optionally in the presence of an acid (suitable acids as for process (f)) and in the presence of triethylsilane.
  • Suitable diluents for carrying out process (g) according to the invention are all inert organic solvents. These preferably include nitriles, such as acetonitrile, propionitrile, n- or iso-butyronitrile or benzonitrile or amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide.
  • nitriles such as acetonitrile, propionitrile, n- or iso-butyronitrile or benzonitrile
  • amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide.
  • Process (g) according to the invention is optionally carried out in the presence of a suitable acid acceptor.
  • a suitable acid acceptor All conventional inorganic or organic bases are suitable as such. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide , Potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N- Dimethyl-benzylamine, pyridine, N-methylpiperidine, N-
  • Process (g) according to the invention is carried out in the presence of one or more catalysts.
  • Palladium salts or complexes are particularly suitable for this.
  • Palladium chloride, palladium acetate, tetrakis (triphenylphosphine) palladium or bis (triphenylphosphine) palladium dichloride are preferred for this purpose.
  • a palladium complex can also be generated in the reaction mixture if a palladium salt and a complex ligand are added separately to the reaction.
  • Organophosphorus compounds are preferred as ligands.
  • Examples include: triphenylphosphine, tri-o-tolylphosphine, 2,2'-bis (diphenylphosphino) -l, -binaphthyl, dicyclohexylphosphine biphenyl, 1,4-bis (diphenylphosphino) butane, bisdiphenylphosphinoferrocene, di (tert-butylphosphino) biphenyl, di (cyclohexylphosphino) biphenyl, 2-dicyclohexylphosphino-2'-N, N-dimethylaminobiphenyl, tricyclohexylphosphine, ttri-tert-butylphosphine.
  • ligands can also be dispensed with.
  • Process (g) according to the invention is also optionally carried out in the presence of a further metal salt, such as copper salts, for example copper (I) iodide.
  • a further metal salt such as copper salts, for example copper (I) iodide.
  • reaction temperatures can be varied within a substantial range when carrying out process (g) according to the invention. In general, temperatures from 20 ° C to 180 ° C, preferably at temperatures from 50 ° C to 150 ° C.
  • Suitable diluents for carrying out process (h) according to the invention are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Nitriles, like Acet
  • Process (h) according to the invention is optionally carried out in the presence of a suitable acid acceptor.
  • a suitable acid acceptor preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates or alkali metal hydrocarbon compounds, such as, for example, sodium hydride, sodium hydroxide, potassium hydroxide, sodium amide, lithium diisopropylamide, sodium methylate, sodium ethylate, potassium tert-butoxide, methylitium , Phenyllitium or butyllitium.
  • reaction temperatures can be varied within a substantial range when carrying out process (h) according to the invention. In general, temperatures from -80 ° C to 150 ° C, preferably at temperatures from -30 ° C to 80 ° C.
  • Suitable diluents for carrying out process (i) according to the invention are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole or amides, such as N
  • Process (i) according to the invention is carried out in the presence of a base.
  • a base preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or
  • bicarbonates such as sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or cesium carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethyl-benzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecen (DBU).
  • DABCO diazabicyclooctane
  • DBN diazabicyclonones
  • DBU
  • reaction temperatures can be varied within a substantial range when carrying out process (i) according to the invention. In general, temperatures from 0 ° C to 150 ° C, preferably at temperatures from 20 ° C to 110 ° C.
  • 0.2 to 5 mol, preferably 0.5 to 2 mol, of halide of the formula (XTTT) are generally employed per mole of the iodopyrazolylcarboxanilide of the formula (Ib) ) on.
  • All processes according to the invention are generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure - generally between 0.1 bar and 10 bar.
  • the substances according to the invention have a strong microbicidal action and can be used to control unwanted microorganisms, such as fungi and bacteria, in crop protection and in material protection.
  • Fungicides can be used to protect plants against Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
  • Bactericides can be used in crop protection to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
  • Xanthomonas species such as, for example, Xanthomonas campestris pv. Oryzae
  • Pseudomonas species such as, for example, Pseudomonas syringae pv. Lachrymans
  • Erwinia species such as, for example, Erwinia amylovora
  • Pythium species such as, for example, Pythium ultimum
  • Phytophthora species such as, for example, Phytophthora infestans
  • Pseudoperonospora species such as, for example, Pseudoperonospora humuli or
  • Plasmopara species such as, for example, Plasmopara viticola
  • Bremia species such as, for example, Bremia lactucae
  • Peronospora species such as, for example, Peronospora pisi or P. brassicae
  • Peronospora species such as, for example, Peronospora pisi or P. brassicae
  • Erysiphe species such as, for example, Erysiphe graminis
  • Sphaerotheca species such as, for example, Sphaerotheca fuliginea
  • Podosphaera species such as, for example, Podosphaera leucotricha
  • Venturia species such as, for example, Venturia inaequalis
  • Pyrenophora species such as, for example, Pyrenophora teres or P. graminea
  • Drechslera (Conidial form: Drechslera, Syn: Helminthosporium);
  • Cochliobolus species such as, for example, Cochliobolus sativus
  • Drechslera (Conidial form: Drechslera, Syn: Helminthosporium);
  • Uromyces species such as, for example, Uromyces appendiculatus
  • Puccinia species such as, for example, Puccinia recondita
  • Sclerotinia species such as, for example, Sclerotinia sclerotiorum
  • Tilletia species such as, for example, Tilletia caries
  • Ustilago species such as, for example, Ustilago nuda or Ustilago avenae;
  • Pellicularia species such as, for example, Pellicularia sasakii
  • Pyricularia species such as, for example, Pyricularia oryzae
  • Fusarium species such as, for example, Fusarium culmorum
  • Botrytis species such as, for example, Botrytis cinerea
  • Septoria species such as, for example, Septoria nodorum
  • Leptosphaeria species such as, for example, Leptosphaeria nodorum
  • Cercospora species such as, for example, Cercospora canescens
  • Alternaria species such as, for example, Alternaria brassicae;
  • Pseudocercosporella species such as, for example, Pseudocercosporella herpotrichoides.
  • the active compounds according to the invention also have a strong strengthening effect in plants. They are therefore suitable for mobilizing the plant's own defenses against attack by unwanted microorganisms.
  • Plant-strengthening (resistance-inducing) substances are to be understood in the present context as substances which are able to stimulate the defense system of plants in such a way that the treated plants develop extensive resistance to these microorganisms when subsequently inoculated with undesired microorganisms.
  • Undesired microorganisms are to be understood in the present case as phytopathogenic fungi, bacteria and viruses.
  • the substances according to the invention can thus be used to protect plants against attack by the pests mentioned within a certain period of time after the treatment.
  • the period of time within which protection is brought about generally extends from 1 to 10 days, preferably 1 to 7 days, after the plants have been treated with the active compounds.
  • the active compounds according to the invention can be used with particularly good success for combating cereal diseases, for example against Puccinia species and for diseases in wine, fruit and vegetable cultivation, for example for botrytis, Venturia or Alternaria species.
  • the active compounds according to the invention are also suitable for increasing the crop yield. They are also less toxic and have good plant tolerance.
  • the active compounds according to the invention can 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 compounds.
  • Plants are understood here to mean 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 cultivars which can or cannot be protected by plant breeders' rights.
  • Plant parts are to be understood to mean all above-ground and underground parts and organs of plants, such as shoots, leaves, flowers and roots, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes.
  • the plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.
  • the treatment of the plants and parts of plants with the active compounds according to the invention is carried out directly or by acting on their surroundings, living space or storage space according to the customary methods
  • Treatment methods e.g. by dipping, spraying, vaporizing, atomizing, scattering, spreading and, in the case of propagation material, in particular in the case of seeds, furthermore by coating in one or more layers.
  • the substances according to the invention can be used to protect technical materials against attack and destruction by undesired microorganisms.
  • technical materials are understood to mean non-living materials that have been prepared for use in technology.
  • technical materials which are to be protected against microbial change or destruction by active substances according to the invention can be adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which are attacked or decomposed by microorganisms can be.
  • parts of production systems for example cooling water circuits, are also mentioned which can be impaired by the multiplication of microorganisms.
  • technical materials are preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer liquids, particularly preferably wood.
  • Bacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can cause degradation or a change in the technical materials.
  • the active compounds according to the invention preferably act against fungi, in particular mold, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.
  • Microorganisms of the following genera may be mentioned, for example:
  • Alternaria such as Alternaria tenuis, Aspergillus, such as Aspergillus niger,
  • Chaetomium like Chaetomium globosum
  • Coniophora such as Coniophora puetana
  • Lentinus such as Lentinus tigrinus
  • Penicillium such as Penicillium glaucum
  • Polyporus such as Polyporus versicolor
  • Aureobasidium such as Aureobasidium pullulans
  • Sclerophoma such as Sclerophoma pityophila
  • Trichoderma like Trichoderma viride
  • Escherichia such as Escherichia coli
  • Pseudomonas such as Pseudomonas aeruginosa
  • Staphylococcus such as Staphylococcus aureus.
  • the active ingredients can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV -Cold and warm mist formulations.
  • formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents.
  • extenders that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • surface-active agents that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can, for example, also be used as auxiliary solvents.
  • aromatics such as xylene, toluene or alkylnaphthalenes
  • chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
  • aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions
  • alcohols such as butanol or glycol and their ethers and esters
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone
  • strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide.
  • Solid carrier materials come into question: for example natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates.
  • Solid carriers for granules are possible: e.g.
  • emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates.
  • Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
  • the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to to broaden the spectrum of activity or to prevent the development of resistance.
  • fungicides bactericides
  • acaricides nematicides or insecticides
  • synergistic effects are obtained, i.e. the effectiveness of the mixture is greater than the effectiveness of the individual components.
  • iprodione iprovalicarb
  • Irumamycin isoprothiolane
  • Isovaledione kasugamycin
  • Kresoxim-methyl iprodione; iprovalicarb; Irumamycin; isoprothiolane; Isovaledione; kasugamycin; Kresoxim-methyl;
  • mancozeb maneb; Meferimzone; mepanipyrim; mepronil; metalaxyl; Metalaxyl-M; metconazole;
  • methasulfocarb Methfuroxam; metiram; metominostrobin; Metsulfovax; mildiomycin; Myclobutanil; myclozoline; natamycin; nicobifen; Nitro Thal-isopropyl; Noviflumuron; nuarimol; ofurace;
  • orysastrobin oxadixyl; Oxolinic acid; Oxpoconazole; oxycarboxin; Oxyfenthiin; paclobutrazol;
  • Pefurazoate Pefurazoate; penconazole; pencycuron; phosdiphen; phthalides; picoxystrobin; piperalin; Polyoxins;
  • Butathiofos Butocarboxim, Butoxycarboxim, Butylpyridaben, Cadusafos, Camphechlor, Carbaryl,
  • Pirimiphos-methyl Pirimiphos-ethyl
  • Prallethrin Profenofos
  • Propetamphos Propoxur, Prothiofos, Prothoate, Protrifenbute, Pymetrozine, Pyraclofos, Pyresmethrin, Pyrethrum, Pyridaben, Pyridalyl, Pyridaphenthion, Pyridathion, Pyrimidifen, Pyriproxyfen, Quinalphos, Resmethrin, RH -725, RU-575, RU-575, RU-575, RU-575, RU-575, RU-R525, RU-575, RU-575, RU-R525, RU-255, RU-575, RU-R525, RU-255 S-421, S-1833, Salithion,
  • the compounds of the formula (I) according to the invention also have very good antifungal effects. They have a very broad spectrum of antifungal effects, in particular against dermatophytes and shoot fungi, mold and diphasic fungi (e.g. against Candida species such as Candida albicans, Candida glabrata) as well as Epidermophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillichophophophytony fumigton, fumigatus and Fumigyus mentagrophytes, microsporon species such as microsporon canis and audouinii.
  • Candida species such as Candida albicans, Candida glabrata
  • Epidermophyton floccosum Aspergillus species such as Aspergillus niger and Aspergillichophophytony fumigton, fumigatus and Fumigyus mentagrophytes
  • microsporon species such as microsporon canis and audouinii.
  • the active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the customary manner, for example by watering, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to remove the active ingredients using the ultra-low-volume process. bring or inject the drug preparation or the drug itself into the soil. The seeds of the plants can also be treated.
  • the application rates can be varied within a relatively wide range, depending on the type of application.
  • the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha.
  • the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed.
  • the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.
  • all plants and their parts can be treated.
  • wild plant species or plant species and their parts obtained by conventional biological breeding methods such as crossing or protoplast fusion
  • transgenic plants and plant cultivars which have been obtained by genetic engineering methods if appropriate in combination with conventional methods (genetically modified organisms) and their parts are treated.
  • the term “parts” or “parts of plants” or “parts of plants” was explained above.
  • Plants of the plant varieties which are in each case commercially available or in use are particularly preferably treated according to the invention.
  • Plant cultivars are understood to mean plants with new properties (“traits”) which have been cultivated by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be cultivars, breeds, bio- and genotypes.
  • the treatment according to the invention can also result in superadditive (“synergistic”) effects.
  • superadditive for example, reduced application rates and or widening the spectrum of action and / or strengthening the effect of the substances and agents which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to dryness or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripeness, higher harvest yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or workability of the harvested products possible, which is actually about the expected effects go beyond.
  • the preferred transgenic plants or plant cultivars to be treated according to the invention include all plants which have received genetic material through the genetic engineering modification, which gives these plants particularly advantageous valuable properties (“traits”). Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripeness, higher harvest yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or Machinability of the harvested products Further and particularly highlighted examples of such properties are an increased defense of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and / or vire n and an increased tolerance of the plants to certain herbicidal active ingredients.
  • transgenic plants are the important cultivated plants, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, tobacco, rapeseed and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with corn, soybeans, potatoes , Cotton, tobacco and rapeseed are highlighted.
  • the traits are particularly emphasized as the increased defense of the plants against insects, arachnids, namatodes and snails by toxins which arise in the plants, in particular those which are caused by the genetic material from Bacillus thuringiensis (eg by the genes Cry ⁇ A (a) , CryIA (b), Cry ⁇ A (c), CryllA, CrylHA, CryIHB2, Cry9c Cry2Ab, Cry3Bb and CrylF as well as their combinations) are produced in the plants (hereinafter referred to as "Bt plants”).
  • Bacillus thuringiensis eg by the genes Cry ⁇ A (a) , CryIA (b), Cry ⁇ A (c), CryllA, CrylHA, CryIHB2, Cry9c Cry2Ab, Cry3Bb and CrylF as well as their combinations
  • Trans are also used the increased defense of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors as well as resistance genes and correspondingly expressed proteins and toxins are particularly emphasized.
  • SAR systemic acquired resistance
  • the properties (“traits”) which are particularly emphasized are the increased tolerance of the plants to certain herbicidal active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (for example “PAT” gene).
  • the genes conferring the desired properties (“traits”) can also occur in combinations with one another in the transgenic plants.
  • Bt plants are maize varieties, cotton varieties, soy varieties and potato varieties that are marketed under the trade names YIELD GARD® (e.g. corn, cotton, soy), KnockOut® (e.g. corn), StarLink® (e.g. corn), Bollgard® ( Cotton), Nucoton® (cotton) and NewLeaf® (potato).
  • herbicide-tolerant plants are maize varieties, cotton varieties and soy varieties that are marketed under the trade names Roundup Ready® (tolerance to glyphosate e.g. corn, cotton, soy), Liberty Link® (tolerance to phosphinotricin, e.g.
  • rapeseed rapeseed
  • IMI® tolerance to Imidazolinone
  • STS® tolerance to sulfonylureas such as maize
  • the herbicide-resistant plants include the varieties sold under the name Clearfield® (eg maize). Of course, these statements also apply to plant varieties developed in the future or coming onto the market in the future with these or future-developed genetic properties ("traits").
  • plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula (I) or the active compound mixtures according to the invention.
  • the preferred ranges given above for the active substances or mixtures also apply to the treatment of these plants. Plant treatment with the compounds or mixtures specifically listed in the present text should be particularly emphasized.
  • Step 2 A solution of 29.0 g (189 mmol) of 2-difluoromethyl-benzonitrile in 700 mL 4% sodium hydroxide solution was heated under reflux for 6 hours. The reaction mixture was cooled to room temperature, poured onto ice and acidified with concentrated hydrochloric acid. The precipitate was filtered off and dried. 19.3 g (58% of theory) of 2-difluoromethylbenzoic acid were obtained in
  • the specified logP values were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a phase reversal column (C 18).
  • Eluents for determination in the acidic range (pH 2.3): 0.1% aqueous phosphoric acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile.
  • the lambda max values were determined on the basis of the UV spectra from 200 nm to 400 nm in the maxima of the chromatographic signals. applications
  • Botrytis test (bean) / protective
  • dimethylacetamide emulsifier 1 part by weight of alkyl aryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
  • compounds 3 and 4 of the preparation examples show an efficiency of 95% or better at an application rate of 500 g / ha.
  • Emulsifier 0.6 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
  • the plants are then placed in a greenhouse at a temperature of approximately 20.degree. C. and a relative atmospheric humidity of 80% in order to promote the development of rust pustules.
  • Evaluation is carried out 10 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.
  • compound no. 5 of the preparation examples show an efficiency of 100% at an application rate of 500 g / ha.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
  • Evaluation is carried out 7 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

Abstract

The invention relates to novel difluoromethylbenzanilides of formula (I), wherein R1, R2, R3, R4, R5 and Z have the meanings cited in the description. The invention also relates to several methods for the production of said substances and the use thereof in order to combat undesired micro-organisms, and to novel intermediate products and the use thereof.

Description

DIFLUORMETHYLBENZANILIDE UND DEREN VERWENDUNG ZUR BEKÄMPFUNG VON MIKROORGANISMEN, SOWIE ZWISCHENPRODUKTE UND DEREN HERSTELLUNG D IFLUORMETHYLBENZANILIDES AND THEIR USE FOR COMBATING MICROORGANISMS, AND INTERMEDIATE PRODUCTS AND THEIR PRODUCTION
Die vorliegende Erfindung betrifft neue Difluormethylbenzanilide, mehrere Verfahren zu deren Her- Stellung und deren Verwendung zur Bekämpfung von unerwünschten Mikroorganismen.The present invention relates to new difluoromethylbenzanilides, several processes for their preparation and their use for controlling unwanted microorganisms.
Es ist bereits bekannt, dass zahlreiche Carboxanilide fungizide Eigenschaften besitzen (vgl. EP-A 0 545 099, JP-A 2001-302605, JP-A 8-176112). So sind aus EP-A 0 554099 bereits N-(4'-Fluor-l,l'- biphenyl-2-yl)-2-(trifluormethyl)benzamid und N-(2-5ec-Butylphenyl)-2-(trifluormethyl)benzamid bekannt. Die Wirksamkeit dieser Stoffe ist gut, lässt aber in manchen Fällen, z.B. bei niedrigen Aufwandmengen zu wünschen übrig. Difluormethylbenzanilide sind bisher nicht bekannt geworden.It is already known that numerous carboxanilides have fungicidal properties (cf. EP-A 0 545 099, JP-A 2001-302605, JP-A 8-176112). EP-A 0 554099 already includes N- (4'-fluoro-l, l'-biphenyl-2-yl) -2- (trifluoromethyl) benzamide and N- (2-5ec-butylphenyl) -2- (trifluoromethyl) ) known benzamide. The effectiveness of these substances is good, but in some cases, e.g. to be desired at low application rates. Difluoromethylbenzanilides have so far not become known.
Es wurden nun neue Difluormethylbenzanilide der Formel (I)New difluoromethylbenzanilides of the formula (I)
gefunden, in welcher found in which
R1, R2, R3 und R4 unabhängig voneinander für Wasserstoff, Fluor, Chlor, Methyl, iso-Propyl oderR 1 , R 2 , R 3 and R 4 independently of one another for hydrogen, fluorine, chlorine, methyl, iso-propyl or
Methylthio stehen, R5 für Wasserstoff, C C8-Alkyl, Cι-C6-Alkylsulfmyl, C C6-Alkylsulfonyl, C,-C4-Alkoxy-Cι- C4-alkyl, C3-C8-Cycloalkyl; Cι-C6-Halogenalkyl, - -Halogenalkylthio, C C4-Halogenal- kylsulfinyl, Cι-C4-Halogenalkylsulfonyl, Halogen-Cι-C4-alkoxy-Cι-C -alkyl, C3-C8-Halo- gencycloalkyl mit jeweils 1 bis 9 Fluor-, Chlor- und/ oder Bromatomen, Formyl-C C3-alkyl, (C C3-Alkyl)carbonyl-C C3-alkyl, (Cι-C3-Alkoxy)carbonyl-Cι-C3-alkyl; (C C3-Halogenal- kyl)carbonyl-Cι-C3-alkyl, (Cι-C3-Halogenalkoxy)carbonyl-Cj-C3-alkyl mit jeweils 1 bis 7 Fluor-, Chlor- und/ oder Bromatomen, (CrC3-Alkyl)carbonyl-Cι-C3-halogenalkyl, ( -C3- Alkoxy)carbonyl-Cι-C3-halogenalkyl mit jeweils 1 bis 6 Fluor-, Chlor- und/oder Bromatomen, (Cι-C3-Halogenalkyl)carbonyl-Cι-C3-halogenalkyl, (Cι-C3-Halogenalkoxy)carbo- nyl-C C3-halogenalkyl mit jeweils 1 bis 13 Fluor-, Chlor- und/oder Bromatomen; -COR6, -COΝR7R8 oder -CH2NR9R10 steht, R6 für Wasserstoff, d- -Alkyl, CrC8-Alkoxy, C C4-Alkoxy-Cι-C4-alkyl, C3-C8-Cycloalkyl; C C6-Halogenalkyl, Cι-C6-Halogenalkoxy, Halogen-Cι-C4-alkoxy-Cι-C4-alkyl, C3-C8-Are methylthio, R 5 is hydrogen, CC 8 -alkyl, -C-C 6 -alkylsulfmyl, CC 6 -alkylsulfonyl, C, -C 4 -alkoxy-Cι- C 4 alkyl, C 3 -C 8 cycloalkyl; -C-C 6 -haloalkyl, - -haloalkylthio, CC 4 -haloalkyl -sulfinyl, Cι-C 4 -haloalkylsulfonyl, halogen-Cι-C 4 -alkoxy-Cι-C -alkyl, C 3 -C 8 -halo-cycloalkyl with in each case 1 to 9 fluorine, chlorine and / or bromine atoms, formyl-C 3 -alkyl, (CC 3 -alkyl) carbonyl-C 3 -alkyl, (-CC 3 alkoxy) carbonyl -CC 3 alkyl; (CC 3 -Halogenal- alkyl) carbonyl-Cι-C3-alkyl, (Cι-C3-haloalkoxy) carbonyl-Cj-C 3 alkyl each having 1 to 7 fluorine, chlorine and / or bromine atoms, (C r C 3 alkyl) carbonyl -C 3 C 3 haloalkyl, (C 3 alkoxy) carbonyl C 3 C 3 haloalkyl each having 1 to 6 fluorine, chlorine and / or bromine atoms, (C 3 -C 3 haloalkyl) carbonyl-Cι-C 3 haloalkyl, (Cι-C3-haloalkoxy) carbonyl-C C 3 haloalkyl having in each case 1 to 13 fluorine, chlorine and / or bromine atoms; -COR 6 , -COΝR 7 R 8 or -CH 2 NR 9 R 10 , R 6 represents hydrogen, d- -alkyl, C r C 8 -alkoxy, CC 4 -alkoxy-Cι-C 4 -alkyl, C 3 -C 8 cycloalkyl; CC 6 -haloalkyl, -C-C 6 -haloalkoxy, halogen -CC-C 4 -alkoxy-Cι-C 4 -alkyl, C 3 -C 8 -
Halogencycloalkyl mit jeweils 1 bis 9 Fluor-, Chlor- und/oder Bromatomen; -COR11 steht, R7 und R8 unabhängig voneinander für Wasserstoff, Cι-C8-Alkyl, C C4-Alkoxy-Cι-C4-alkyl, C3-C8- Cycloalkyl; C C8-Halogenalkyl, Halogen-Cι-C -alkoxy-Cι-C4-alkyl, C3-C8-Halogencyclo- al yl mit jeweils 1 bis 9 Fluor-, Chlor- und/oder Bromatomen stehen,Halogencycloalkyl each with 1 to 9 fluorine, chlorine and / or bromine atoms; -COR 11 stands, R 7 and R 8 independently of one another for hydrogen, -CC 8 -alkyl, CC 4 -alkoxy -CC-C 4 alkyl, C 3 -C 8 - cycloalkyl; CC 8 -haloalkyl, halo -CC -alkoxy -CC-C 4 -alkyl, C 3 -C 8 -halogenocycloal yl each having 1 to 9 fluorine, chlorine and / or bromine atoms,
R7 und R8 außerdem gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, einen gegebenen- falls einfach oder mehrfach, gleich oder verschieden durch Halogen oder CrC4-Alkyl substituierten gesättigten Heterocyclus mit 5 bis 8 Ringatomen bilden, wobei derR 7 and R 8 together with the nitrogen atom to which they are attached also form a saturated or heterocycle which has 5 to 8 ring atoms and may be mono- or polysubstituted, identically or differently, by halogen or C r C 4 -alkyl, where the
Heterocyclus 1 oder 2 weitere, nicht benachbarte Heteroatome aus der Reihe Sauerstoff,Heterocycle 1 or 2 further, non-adjacent heteroatoms from the series oxygen,
Schwefel oder NR12 enthalten kann,Can contain sulfur or NR 12 ,
R9 und R10 unabhängig voneinander für Wasserstoff, Cι-C8-Alkyl, C3-C8-Cycloalkyl; C C8-Halogen- al yl, C3-C3-Halogencycloalkyl mit jeweils 1 bis 9 Fluor-, Chlor- und/oder Bromatomen stehen,R 9 and R 10 independently of one another for hydrogen, -CC 8 alkyl, C 3 -C 8 cycloalkyl; CC 8 halogen al yl, C 3 -C 3 halocycloalkyl each having 1 to 9 fluorine, chlorine and / or bromine atoms,
R9 und R10 außerdem gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, einen gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Halogen oder Cι-C -Alkyl substituierten gesättigten Heterocyclus mit 5 bis 8 Ringatomen bilden, wobei der Hetero- cyclus 1 oder 2 weitere, nicht benachbarte Heteroatome aus der Reihe Sauerstoff, Schwefel oder NR12 enthalten kann,R 9 and R 10, together with the nitrogen atom to which they are attached, form a saturated heterocycle having 5 to 8 ring atoms, which is optionally mono- or polysubstituted, identically or differently, by halogen or -CC alkyl, the heterocycle 1 or can contain 2 further, non-adjacent heteroatoms from the series oxygen, sulfur or NR 12 ,
R11 für Wasserstoff, C C8-Alkyl, - -Alkoxy, CrC4-Alkoxy-C1-C4-alkyl, C3-C8-Cycloalkyl; Cι-C6-Halogenalkyl, d-C6-Halogenalkoxy, Halogen-Cι-C -alkoxy-Cι-C -alkyl, C3-C8- Halogencycloalkyl mit jeweils 1 bis 9 Fluor-, Chlor- und oder Bromatomen steht, R12 für Wasserstoff oder Ci-Cg-Alkyl steht,R 11 is hydrogen, CC 8 alkyl, - alkoxy, C r C 4 alkoxy-C 1 -C 4 alkyl, C 3 -C 8 cycloalkyl; C 1 -C 6 -haloalkyl, dC 6 -haloalkoxy, halogen-C 1 -C 8 -alkoxy-C 1 -C 8 -alkyl, C 3 -C 8 - halocycloalkyl, each with 1 to 9 fluorine, chlorine and or bromine atoms, R 12 represents hydrogen or Ci-Cg-alkyl,
Z für Z\ Z2, Z3 oder Z4 steht, worinZ stands for Z \ Z 2 , Z 3 or Z 4 , wherein
Z1 für gegebenenfalls einfach bis fünffach, gleich oder verschieden substituiertes Phenyl steht,Z 1 represents phenyl which is monosubstituted to pentas, identical or differently substituted,
Z2 für gegebenenfalls einfach oder mehrfach, gleich oder verschieden substituiertes Cycloalkyl oder Bicycloalkyl steht, Z3 für unsubstituiertes C2-C2o-Alkyl oder für einfach oder mehrfach, gleich oder verschieden durch Halogen und/oder C3-C6-Cycloalkyl substituiertes - o-Alkyl steht, wobei der Cycloalkylteil seinerseits gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Halogen und/oder CrC4-Alkyl substituiert sein kann,Z 2 is optionally monosubstituted or polysubstituted by identical or different substituents, cycloalkyl or bicycloalkyl, Z 3 represents unsubstituted C 2 -C 2 o alkyl or mono- or polysubstituted, identically or differently, by halogen and / or C 3 -C 6 cycloalkyl substituted - o-alkyl, where the cycloalkyl part in turn can optionally be substituted one or more times, identically or differently, by halogen and / or C r C 4 alkyl,
Z4 für jeweils gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Halogen und/oder C3-C6-Cycloalkyl substituiertes C2-C20-Alkenyl oder C2-C2o-Alkinyl steht, wobei der Cycloalkylteil seinerseits gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Halogen und/oder Cι-C4-Alkyl substituiert sein kann, oderZ 4 represents C 2 -C 20 alkenyl or C 2 -C 2 o-alkynyl which is optionally mono- or polysubstituted, identically or differently, by halogen and / or C 3 -C 6 -cycloalkyl, the cycloalkyl part in turn optionally single or can be substituted several times, identically or differently by halogen and / or C 1 -C 4 alkyl, or
R1, R2 und R3 unabhängig voneinander für Wasserstoff oder Fluor stehen und Z und R4 gemeinsam mit den Kohlenstoffatomen, an die sie gebunden sind, einen gegebenenfalls substituierten 5- oder 6-gliedrigen carbocyclischen oder heterocyclischen Ring bilden. Weiterhin wurde gefunden, dass man Difluormethylbenzanilide der Formel (I) erhält, indem man a) Difluormethylbenzoyl-Derivate der Formel (II)R 1 , R 2 and R 3 independently represent hydrogen or fluorine and Z and R 4 together with the carbon atoms to which they are attached form an optionally substituted 5- or 6-membered carbocyclic or heterocyclic ring. It has furthermore been found that difluoromethylbenzanilides of the formula (I) are obtained by a) difluoromethylbenzoyl derivatives of the formula (II)
in welcher in which
X1 für Chlor oder Hydroxy steht, mit Anilin-Derivaten der Formel (HI)X 1 represents chlorine or hydroxy, with aniline derivatives of the formula (HI)
in welcher R , R2, R3, R4, R und Z die oben angegebenen Bedeutungen haben, gegebenenfalls in Gegenwart eines Katalysators, gegebenenfalls in Gegenwart eines Konden- sationsmittels, gegebenenfalls in Gegenwart eines Säurebindemittels und gegebenenfalls in in which R, R 2 , R 3 , R 4 , R and Z have the meanings given above, optionally in the presence of a catalyst, optionally in the presence of a condensing agent, optionally in the presence of an acid binder and optionally in
Gegenwart eines Verdünnungsmittels umsetzt, oder b) Halogen-difluormethylbenzanilide der Formel (IV)Reacting the presence of a diluent, or b) halodifluoromethylbenzanilides of the formula (IV)
in welcher in which
R1, R2, R3, R4 und R5 die oben angegebenen Bedeutungen haben, und X2 für Chlor, Brom, Iod oder Trifluormethylsulfonat steht, mit Boronsäure-Derivaten der Formel (V)R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given above, and X 2 represents chlorine, bromine, iodine or trifluoromethyl sulfonate, with boronic acid derivatives of the formula (V)
in welcher in which
Z1 die oben angegebene Bedeutung hat undZ 1 has the meaning given above and
A1 und A2 jeweils für Wasserstoff oder zusammen für Tetramethylethylen stehen, in Gegenwart eines Katalysators, gegebenenfalls in Gegenwart eines Säurebindemittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder c) Difluormethylbenzamid-Boronsäure-DA 1 and A 2 each represent hydrogen or together represent tetramethylethylene, in the presence of a catalyst, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or c) difluoromethylbenzamide-boronic acid-D
in welcher R1, R2, R3, R4 und R5 die oben angegebenen Bedeutungen haben, und in which R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given above, and
A3 und A4 jeweils für Wasserstoff oder zusammen für Tetramethylethylen stehen, mit Phenyl-Derivaten der Formel (VII) X3— Z1 ( Q) in welcher Z1 die oben angegebenen Bedeutungen hat undA 3 and A 4 each represent hydrogen or together represent tetramethylethylene, with phenyl derivatives of the formula (VII) X 3 - Z 1 (Q) in which Z 1 has the meanings given above and
X3 für Chlor, Brom, Iod oder Trifluormethylsulfonat steht, in Gegenwart eines Katalysators, gegebenenfalls in Gegenwart eines Säurebindemittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder d) Halogen-difluormethylbenzanilide der Formel (TV)X 3 represents chlorine, bromine, iodine or trifluoromethyl sulfonate, in the presence of a catalyst, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or d) halodifluoromethylbenzanilides of the formula (TV)
in welcher in which
R1, R2, R3, R4 und R5 die oben angegebenen Bedeutungen haben, und X2 für Chlor, Brom, Iod oder Trifluormethylsulfonat steht, mit Phenyl-Derivaten der Formel (VII)R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given above, and X 2 represents chlorine, bromine, iodine or trifluoromethyl sulfonate, with phenyl derivatives of the formula (VII)
X3— Z1 (VII) in welcherX 3 - Z 1 (VII) in which
Z1 die oben angegebenen Bedeutungen hat undZ 1 has the meanings given above and
X3 für Chlor, Brom, Iod oder Trifluormethylsulfonat steht, in Gegenwart eines Palladium- oder Nickel-Katalysators und in Gegenwart vonX 3 represents chlorine, bromine, iodine or trifluoromethyl sulfonate, in the presence of a palladium or nickel catalyst and in the presence of
4,4,4,,4,,5,5,5',5,-Octamethyl-2,2,-bis-l,3,2-dioxaborolan, gegebenenfalls in Gegenwart eines Säurebindemittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder e) Difluormethylbenzanilide der Formel (Ia) 4,4,4,, 4,, 5,5,5 ', 5, -Octamethyl-2,2, -bis-l, 3,2-dioxaborolane, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or e) difluoromethylbenzanilides of the formula (Ia)
in welcher R1, R2, R3, R4 und R5 die oben angegebenen Bedeutungen haben und in which R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given above and
X4 für jeweils gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Halogen und/oder C3-C6-Cycloalkyl substituiertes C2-C2o-Alkenyl oder C2-C2o- Alkinyl steht, wobei der Cycloalkylteil seinerseits gegebenenfalls durch Halogen und/oder CrC4-Alkyl substituiert sein kann, gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Katalysators hydriert, oder f) Hydroxyalkyl-difluormethylbenzanilide der Formel (VIII)X 4 stands for C 2 -C 2 o-alkenyl or C 2 -C 2 o-alkynyl which is optionally mono- or polysubstituted, identically or differently, by halogen and / or C 3 -C 6 -cycloalkyl, the cycloalkyl part in turn being optionally substituted by Halogen and / or C r C 4 alkyl may be substituted, optionally hydrogenated in the presence of a diluent and optionally in the presence of a catalyst, or f) hydroxyalkyl-difluoromethylbenzanilides of the formula (VIII)
in welcher in which
R1, R2, R3, R4 und R5 die oben angegebenen Bedeutungen haben und X5 für gegebenenfalls zusätzlich einfach oder mehrfach, gleich oder verschieden durch Halogen und/oder C3-C6-Cycloalkyl substituiertes C2-C2o-Hydroxyalkyl steht, wobei der Cycloalkylteil seinerseits gegebenenfalls durch Halogen und/oder Cι-C4-Alkyl substituiert sein kann, gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart einer Säure dehydratisiert, oder g) Halogen-difluormethylbenzanilide der Formel (TV)R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given above and X 5 for C 2 -C 2 which is optionally monosubstituted or polysubstituted, identically or differently, by halogen and / or C 3 -C 6 -cycloalkyl stands for o-hydroxyalkyl, where the cycloalkyl part in turn can optionally be substituted by halogen and / or C 1 -C 4 alkyl, optionally dehydrated in the presence of a diluent and optionally in the presence of an acid, or g) halodifluoromethylbenzanilides of the formula (TV)
in welcher in which
R1, R2, R3, R4 und R5 die oben angegebenen Bedeutungen haben, undR 1 , R 2 , R 3 , R 4 and R 5 have the meanings given above, and
X2 für Chlor, Brom, Iod oder Trifluormethylsulfonat steht, mit einem Alkin der Formel (IX) HC≡— A5 (IX), in welcherX 2 represents chlorine, bromine, iodine or trifluoromethyl sulfonate, with an alkyne of the formula (IX) HC≡— A 5 (IX), in which
A5 für jeweils gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Halogen und/oder C3-C6-Cycloalkyl substituiertes C2-Cι8-Alkyl steht, wobei der Cycloalkylteil seinerseits gegebenenfalls durch Halogen und oder CrC4-Alkyl substituiert sein kann, oder einem Alken der Formel (X)A 5 is in each case optionally mono- or polysubstituted, identically or differently, by halogen and / or C 3 -C 6 -cycloalkyl-substituted C 2 -C 8 -alkyl, the cycloalkyl part in turn optionally being substituted by halogen and or C r C 4 -alkyl or an alkene of the formula (X)
in welcher in which
A6, A7 und A8 unabhängig voneinander jeweils für Wasserstoff oder gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Halogen und/oder C3-C6-Cycloalkyl substituiertes Alkyl stehen, wobei der Cycloalkylteil seinerseits gegebenenfalls durch Halogen und/oder Cι-C - Alkyl substituiert sein kann und die Gesamtzahl derA 6 , A 7 and A 8 each independently represent hydrogen or optionally mono- or polysubstituted, identically or differently, alkyl substituted by halogen and / or C 3 -C 6 -cycloalkyl, the cycloalkyl part in turn optionally being substituted by halogen and / or Cι- C - alkyl can be substituted and the total number of
Kohlenstoffatome des offenkettigen Molekülteils die Zahl 20 nicht übersteigt, gegebenenfalls in Gegenwart eines Verdünnungsmittels, gegebenenfalls in Gegenwart eines Säurebindemittels und in Gegenwart eines oder mehrerer Katalysatoren umsetzt, oder h) Ketone der Formel (XI)Carbon atoms of the open-chain part of the molecule does not exceed 20, if appropriate in the presence of a diluent, if appropriate in the presence of an acid binder and in the presence of one or more catalysts, or h) ketones of the formula (XI)
in welcher R1, R2, R3, R4 und R5 die oben angegebenen Bedeutungen haben und in which R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given above and
A9 für Wasserstoff oder gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Halogen und/oder C3- -Cycloalk l substituiertes Cι-Cι8-Alkyl steht, wobei der Cycloalkylteil seinerseits gegebenenfalls durch Halogen undoder C C -Alkyl substituiert sein kann, mit einer Phosphorverbindung der allgemeinen Formel (Xu)A 9 represents hydrogen or optionally mono- or polysubstituted, identically or differently, C 1 -C 8 -alkyl substituted by halogen and / or C 3 -Cycloalk l, where the cycloalkyl part in turn may optionally be substituted by halogen and or CC-alkyl, with a phosphorus compound of the general formula (Xu)
A i°__Px (xπ), in welcher A i ° __ Px (xπ), in which
A10 für gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Halogen und/oder C3-C6-Cycloalkyl substituiertes C Cι8-Alkyl steht, wobei der Cycloalkylteil seinerseits gegebenenfalls durch Halogen und/oder C C4-Al yl substituiert sein kann, Px für eine Gruppierung -P^C^ CF, -P+(C6H5)3 Bf", -P+(C6H5)3 T, -P(=0)(OCH3)3 oder -P(=O)(OC2H5)3 steht, gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder i) Difluormethylbenzanilide der Formel (Ib)A 10 represents C 1 -C 8 -alkyl which is optionally mono- or polysubstituted, identically or differently, by halogen and / or C 3 -C 6 -cycloalkyl, the cycloalkyl part in turn being optionally substituted by halogen and / or CC 4 -al yl, Px for a grouping -P ^ C ^ CF, -P + (C6H 5 ) 3 Bf " , -P + (C 6 H 5 ) 3 T, -P (= 0) (OCH 3 ) 3 or -P (= O) (OC 2 H 5 ) 3 , optionally reacted in the presence of a diluent, or i) difluoromethylbenzanilides of the formula (Ib)
in welcher R1, R2, R3, R4 und Z die oben angegebenen Bedeutungen haben mit einem Halogenid der Formel (XIII) in which R 1 , R 2 , R 3 , R 4 and Z have the meanings given above with a halide of the formula (XIII)
in welcher in which
R5-1 für C,-C8-Alkyl, - -Alkylsulfmyl, C,-C6-Alkylsulfonyl, CrC4-Alkoxy-C C4- alkyl, C3-C8-Cycloalkyl; CrC6-Halogenalkyl, C C4-Halogenalkylthio, C C4-Halo- genalkylsulfϊnyl, C]-C -Halogenalkylsulfonyl, Halogen-Cι-C -alkoxy-CrC4-alkyl,R 5 - 1 for C, -C 8 alkyl, - alkyl sulfmyl, C, -C 6 alkyl sulfonyl, C r C 4 alkoxy-C C 4 alkyl, C 3 -C 8 cycloalkyl; C r C 6 -haloalkyl, CC 4 -haloalkylthio, CC 4 -haloalkylsulfonyl, C] -C -haloalkylsulfonyl, halo -CC -alkoxy-C r C 4 -alkyl,
C3-C8-Halogencycloalkyl mit jeweils 1 bis 9 Fluor-, Chlor- und/oder Bromatomen,C 3 -C 8 halocycloalkyl each having 1 to 9 fluorine, chlorine and / or bromine atoms,
Formyl-Cι-C3-alkyl, (Cι-C3-Alkyl)carbonyl-C C3-alkyl, (C C3-Alkoxy)carbonyl-Formyl -CC 3 -alkyl, (-C 3 -alkyl) carbonyl-C 3 -alkyl, (CC 3 -alkoxy) carbonyl-
Cι-C3-alkyl; (Cι-C3-Halogenalkyl)carbonyl-C C3-alkyl, (C C3-Halogenalkoxy)car- bonyl-C C3-alkyl mit jeweils 1 bis 7 Fluor-, Chlor- und/oder Bromatomen, (C1-C3--C-C 3 alkyl; (Cι-C 3 haloalkyl) carbonyl C-C 3 alkyl, (CC 3 -haloalkoxy) carbonyl-C C 3 alkyl each having 1 to 7 fluorine, chlorine and / or bromine atoms, (C 1 - C 3 -
Alkyl)carbonyl-CrC3-halogenalkyl, (C1-C3-Alkoxy)carbonyl-Cι-C3-halogenalkyl mit jeweils 1 bis 6 Fluor-, Chlor- und/oder Bromatomen, (Cι-C3-Halogenalkyl)car- bonyl-Cι-C3-halogenal yl, (Cι-C3-Halogenalkoxy)carbonyl-Cι-C3-halogenalkyl mit jeweils 1 bis 13 Fluor-, Chlor- und oder Bromatomen; -COR6, -CONR7R8 oder -CH2NR9R10 steht,Alkyl) carbonyl-C r C 3 -haloalkyl, (C 1 -C 3 -alkoxy) carbonyl-Cι-C 3 -haloalkyl each with 1 to 6 fluorine, chlorine and / or bromine atoms, (Cι-C 3 haloalkyl ) carbonyl-Cι-C 3 -halogenal yl, (Cι-C3-haloalkoxy) carbonyl-Cι-C 3 haloalkyl having in each case 1 to 13 fluorine, chlorine and or bromine atoms; -COR 6 , -CONR 7 R 8 or -CH 2 NR 9 R 10 ,
R6, R7, R8, R9 und R10 die oben angegebenen Bedeutungen haben und X6 für Chlor, Brom oder Iod steht, in Gegenwart einer Base und in Gegenwart eines Verdünnungsmittels umsetzt.R 6 , R 7 , R 8 , R 9 and R 10 have the meanings given above and X 6 represents chlorine, bromine or iodine, in the presence of a base and in the presence of a diluent.
Schließlich wurde gefunden, dass die neuen Difluormethylbenzanilide der Formel (I) sehr gute mikrobizide Eigenschaften besitzen und zur Bekämpfung unerwünschter Mikroorganismen sowohl im Pflanzenschutz als auch im Materialschutz verwendbar sind.Finally, it was found that the new difluoromethylbenzanilides of the formula (I) have very good microbicidal properties and can be used to control unwanted microorganisms both in crop protection and in material protection.
Überraschenderweise zeigen die erfϊndungsgemäßen Difluormethylbenzanilide der Formel (I) eine wesentlich bessere fungizide Wirksamkeit als die konstitutionell ähnlichsten, vorbekannten Wirk- Stoffe gleicher Wirkungsrichtung.Surprisingly, the difluoromethylbenzanilides of the formula (I) according to the invention show a substantially better fungicidal activity than the constitutionally most similar, known active substances of the same direction of action.
Die erfrndungsgemäßen Verbindungen können gegebenenfalls als Mischungen verschiedener möglicher isomerer Formen, insbesondere von Stereoisomeren, wie z. B. E- und Z-, threo- und erythro-, sowie optischen Isomeren, gegebenenfalls aber auch von Tautomeren vorliegen. Es werden sowohl die E- als auch die Z-Isomeren, wie auch die threo- und erythro-, sowie die optischen Isomeren, beliebige Mischungen dieser Isomeren, sowie die möglichen tautomeren Formen beansprucht.The compounds according to the invention can optionally be in the form of mixtures of various possible isomeric forms, in particular stereoisomers, such as, for. B. E and Z, threo and erythro, and optical isomers, but optionally also of tautomers are present. Both the E and the Z isomers, as well as the threo and erythro and optical isomers, any mixtures of these isomers and the possible tautomeric forms are claimed.
Die erfindungsgemäßen Difluormethylbenzanilide sind durch die Formel (I) allgemein definiert. Bevorzugte Restedefinitionen der vorstehenden und nachfolgend genannten Formeln sind im Folgenden angegeben. Diese Definitionen gelten für die Endprodukte der Formel (I) wie für alle Zwischenprodukte gleichermaßen.The difluoromethylbenzanilides according to the invention are generally defined by the formula (I). Preferred radical definitions of the formulas mentioned above and below are given below. These definitions apply equally to the end products of the formula (I) and to all intermediates.
R1, R2, R3 und R4 stehen unabhängig voneinander bevorzugt für Wasserstoff, Fluor, Chlor oder Methyl. R1 steht besonders bevorzugt für Wasserstoff oder Fluor.R 1 , R 2 , R 3 and R 4 independently of one another preferably represent hydrogen, fluorine, chlorine or methyl. R 1 particularly preferably represents hydrogen or fluorine.
R1 steht ganz besonders bevorzugt für Wasserstoff.R 1 very particularly preferably represents hydrogen.
R1 steht auch ganz besonders bevorzugt für Fluor.R 1 also very particularly preferably represents fluorine.
R2 steht besonders bevorzugt für Wasserstoff.R 2 particularly preferably represents hydrogen.
R3 steht besonders bevorzugt für Wasserstoff, Fluor, Chlor oder Methylthio. R3 steht ganz besonders bevorzugt für Wasserstoff.R 3 particularly preferably represents hydrogen, fluorine, chlorine or methylthio. R 3 very particularly preferably represents hydrogen.
R3 steht auch ganz besonders bevorzugt für Fluor.R 3 also very particularly preferably represents fluorine.
R4 steht besonders bevorzugt für Wasserstoff, Methyl oder iso-Propyl.R 4 particularly preferably represents hydrogen, methyl or isopropyl.
R4 steht ganz besonders bevorzugt für Wasserstoff.R 4 very particularly preferably represents hydrogen.
R4 steht auch ganz besonders bevorzugt für Methyl. R1, R2, R3 und R4 stehen ganz besonders bevorzugt gleichzeitig für Wasserstoff. R5 steht bevorzugt für Wasserstoff; -C6-Alkyl, C C4-Alkylsulfinyl, d-C4-Alkylsulfonyl, d- C3-Alkoxy-Cι-C3-alkyl, C3-C6-Cycloalkyl; CrC4-Halogenalkyl, d-C4-Halogenalkylthio, d- C -Halogenalkylsulfinyl, C C4-Halogenalkylsulfonyl, Halogen-Cι-C3-alkoxy-C C3-alkyl, C3-Cö-Halogencycloalkyl mit jeweils 1 bis 9 Fluor-, Chlor- und/oder Bromatomen, Formyl- C C3-alkyl, (d-C3-Alkyl)carbonyl-d-C3-alkyl, (C C3-Alkoxy)carbonyl-CrC3-alkyl; (CR 4 also very particularly preferably represents methyl. R 1 , R 2 , R 3 and R 4 very particularly preferably simultaneously represent hydrogen. R 5 preferably represents hydrogen; -C 6 -alkyl, CC 4 -alkylsulfinyl, dC 4 -alkylsulfonyl, d- C3-alkoxy-C 3 -C 3 -alkyl, C 3 -C 6 -cycloalkyl; C r C 4 haloalkyl, dC 4 haloalkylthio, haloalkylsulfinyl dC, CC 4 -haloalkylsulfonyl, halo-Cι-C3-alkoxy-C C 3 alkyl, C 3 -C ö halocycloalkyl having in each case 1 to 9 Fluorine, chlorine and / or bromine atoms, formyl-CC 3 -alkyl, (dC 3 -alkyl) carbonyl-dC 3 -alkyl, (CC 3 -alkoxy) carbonyl-C r C 3 -alkyl; (C
C3-Halogenalkyl)carbonyl-Cι-C3-alkyl, (Cι-C3-Halogenalkoxy)carbonyl-C C3-alkyl mit jeweils 1 bis 7 Fluor , Chlor- und/oder Bromatomen, (C C3-Alkyl)carbonyl-d-C3-halogenal- kyl, (Cι-C3-Alkoxy)carbonyl-Cι-C3-halogenalkyl mit jeweils 1 bis 6 Fluor-, Chlor- und/ oder Bromatomen, (d-d-Halogenalky carbonyl-d-d-halogenalkyl, (C C3-Halogenalkoxy)- carbonyl-C C3-halogenalkyl mit jeweils 1 bis 13 Fluor-, Chlor- und oder Bromatomen;C 3 -haloalkyl) carbonyl -CC 3 -alkyl, (-C-C 3 -haloalkoxy) carbonyl-C C 3 -alkyl each having 1 to 7 fluorine, chlorine and / or bromine atoms, (CC 3 -alkyl) carbonyl -dC 3 -haloalkyl, (-C-C 3 -alkoxy) carbonyl -CC-C 3 -haloalkyl each having 1 to 6 fluorine, chlorine and / or bromine atoms, (dd-haloalky carbonyl-dd-haloalkyl, ( CC 3 -haloalkoxy) - carbonyl-C C 3 -haloalkyl each having 1 to 13 fluorine, chlorine and or bromine atoms;
-COR6, -CONR7R8 oder -CH2NR9R10.-COR 6 , -CONR 7 R 8 or -CH 2 NR 9 R 10 .
R5 steht besonders bevorzugt für Wasserstoff, Methyl, Ethyl, n- oder iso-Propyl, n-, iso-, sec- oder tert-Butyl, Pentyl oder Hexyl, Methylsulfinyl, Ethylsulfinyl, n- oder iso-Propylsulfinyl, n-, iso-, sec- oder tert-Butylsulfinyl, Methylsulfonyl, Ethylsulfonyl, n- oder iso-Propylsulfo- nyl, n-, iso-, sec- oder tert-Butylsulfonyl, Methoxymethyl, Methoxyethyl, Ethoxymethyl,R 5 particularly preferably represents hydrogen, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, pentyl or hexyl, methylsulfinyl, ethylsulfinyl, n- or iso-propylsulfinyl, n-, iso-, sec- or tert-butylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or iso-propylsulfonyl, n-, iso-, sec- or tert-butylsulfonyl, methoxymethyl, methoxyethyl, ethoxymethyl,
Ethoxyethyl, Cyclopropyl, Cyclopentyl, Cyclohexyl, Trifluoimethyl, Trichlormethyl, Trifluorethyl, Difluormethylthio, Difluorchlormethylthio, Trifluormethylthio, Trifluorme- thylsulfmyl, Trifluormethylsulfonyl, Trifluormethoxymethyl, -CH2-CHO, -CH2CH2-CHO, -CH2-CO-CH3, -CH2-CO-CH2CH3, -CH2-CO-CH(CH3)2, -CH2CH2-CO-CH3, -CH2CH2-CO-CH2CH3, -CH2CH2-CO-CH(CH3)2, -CH2-C(0)OCH3, -CH2-C(0)OCH2CH3,Ethoxyethyl, cyclopropyl, cyclopentyl, cyclohexyl, Trifluoimethyl, trichloromethyl, trifluoroethyl, difluoromethylthio, difluorochloromethylthio, trifluoromethylthio, trifluoromethanesulfonic thylsulfmyl, trifluoromethylsulfonyl, trifluoromethoxymethyl, -CH 2 -CHO, -CH 2 CH 2 -CHO, -CH 2 -CO-CH 3 , -CH 2 -CO-CH 2 CH 3 , -CH 2 -CO-CH (CH 3 ) 2 , -CH 2 CH 2 -CO-CH 3 , -CH 2 CH 2 -CO-CH 2 CH 3 , - CH 2 CH 2 -CO-CH (CH 3 ) 2 , -CH 2 -C (0) OCH 3 , -CH 2 -C (0) OCH 2 CH 3 ,
-CH2-C(0)OCH(CH3)2, -CH2CH2-C(0)OCH3, -CH2CH2-C(0)OCH2CH3,-CH 2 -C (0) OCH (CH 3 ) 2 , -CH 2 CH 2 -C (0) OCH 3 , -CH 2 CH 2 -C (0) OCH 2 CH 3 ,
-CH2CH2-C(0)OCH(CH3)2, -CH2-C0-CF3, -CH2-CO-CCl3, -CH2-CO-CH2CF3, -CH2-C0-CH2CC13, -CH2CH2-CO-CH2CF3, -CH2CH2-CO-CH2CCl3, -CH2-C(0)OCH2CF3, -CH2-C(0)OCF2CF3, -CH2-C(0)0CH2CC13, -CH2-C(0)0CC12CC13, -CH2CH2-C(0)0CH2CF3, -CH2CH2-C(0)OCF2CF3, -CH2CH2-C(0)0CH2CC13,-CH 2 CH 2 -C (0) OCH (CH 3 ) 2 , -CH 2 -C0-CF 3 , -CH 2 -CO-CCl 3 , -CH 2 -CO-CH 2 CF 3 , -CH 2 - C0-CH 2 CC1 3 , -CH 2 CH 2 -CO-CH 2 CF 3 , -CH 2 CH 2 -CO-CH 2 CCl 3 , -CH 2 -C (0) OCH 2 CF 3 , -CH 2 - C (0) OCF 2 CF 3 , -CH 2 -C (0) 0CH 2 CC1 3 , -CH 2 -C (0) 0CC1 2 CC1 3 , -CH 2 CH 2 -C (0) 0CH 2 CF 3 , -CH 2 CH 2 -C (0) OCF 2 CF 3 , -CH 2 CH 2 -C (0) 0CH 2 CC1 3 ,
-CH2CH2-C(0)0-CC12CC13; -COR6, -CONR7R8 oder -CH2NR9R10. R5 steht ganz besonders bevorzugt für Wasserstoff; Methyl, Methoxymethyl, -CH2-CHO, -CH2CH2-CHO, -CH2-CO-CH3, -CH2-CO-CH2CH3, -CH2-CO-CH(CH3)2 oder -COR6.-CH 2 CH 2 -C (0) 0-CC1 2 CC1 3 ; -COR 6 , -CONR 7 R 8 or -CH 2 NR 9 R 10 . R 5 very particularly preferably represents hydrogen; Methyl, methoxymethyl, -CH 2 -CHO, -CH 2 CH 2 -CHO, -CH 2 -CO-CH 3 , -CH 2 -CO-CH 2 CH 3 , -CH 2 -CO-CH (CH 3 ) 2 or -COR 6 .
R6 steht bevorzugt für Wasserstoff, C C6-Alkyl, C C4-Alkoxy, C C3-Alkoxy-d-C3-alkyl, C3-R 6 preferably represents hydrogen, CC 6 alkyl, CC 4 alkoxy, CC 3 alkoxy-dC 3 alkyl, C 3 -
C6-Cycloalkyl; Cι-C4-Halogenalkyl, C C4-Halogenalkoxy, Halogen-d-C3-alkoxy-Cι-C3- alkyl, C3-C6-Halogencycloalkyl mit jeweils 1 bis 9 Fluor-, Chlor- und/oder Bromatomen,C 6 cycloalkyl; -C-C 4 haloalkyl, CC 4 -haloalkoxy, halogen-dC 3 -alkoxy-Cι-C 3 alkyl, C 3 -C 6 halocycloalkyl, each with 1 to 9 fluorine, chlorine and / or bromine atoms,
-COR11.-COR 11
R6 steht besonders bevorzugt für Wasserstoff, Methyl, Ethyl, n- oder iso-Propyl, tert-Butyl, Methoxy, Ethoxy, iso-Propoxy, tert-Butoxy, Cyclopropyl; Trifluormethyl, Trifluormethoxy,R 6 particularly preferably represents hydrogen, methyl, ethyl, n- or iso-propyl, tert-butyl, methoxy, ethoxy, iso-propoxy, tert-butoxy, cyclopropyl; Trifluoromethyl, trifluoromethoxy,
-COR11. R6 steht ganz besonders bevorzugt für Wasserstoff, -COCH3, -CHO, -COCH2OCH3,-COR 11 R 6 very particularly preferably represents hydrogen, -COCH 3 , -CHO, -COCH 2 OCH 3 ,
-COC02CH3, -COC02CH2CH3.-COC0 2 CH 3 , -COC0 2 CH 2 CH 3 .
R7 und R8 stehen unabhängig voneinander bevorzugt für Wasserstoff, C C6- Alkyl, d-C3-Alkoxy-Cr C3-alkyl, C3-C6-Cycloalkyl; C,-C4-Halogenalkyl, Halogen-Cι-C3-alkoxy-CrC3-alkyl, C3-C6-R 7 and R 8 independently of one another preferably represent hydrogen, CC 6 -alkyl, dC 3 -alkoxy-C r C 3 -alkyl, C 3 -C 6 -cycloalkyl; C, -C 4 haloalkyl, halo -CC 3 alkoxy-C r C 3 alkyl, C 3 -C 6 -
Halogencycloalkyl mit jeweils 1 bis 9 Fluor-, Chlor- und/oder Bromatomen. R7 und R8 bilden außerdem gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, bevorzugt einen gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Halogen oder C Q-Alkyl substituierten gesättigten Heterocyclus mit 5 bis 8 Ringatomen, wobei der Hetero- cyclus 1 oder 2 weitere, nicht benachbarte Heteroatome aus der Reihe Sauerstoff, Schwefel oder NR12 enthalten kann. R7 und R8 stehen unabhängig voneinander besonders bevorzugt für Wasserstoff, Methyl, Ethyl, n- oder iso-Propyl, n-, iso-, sec- oder tert-Butyl, Methoxymethyl, Methoxyethyl, Ethoxymethyl, Ethoxyethyl, Cyclopropyl, Cyclopentyl, Cyclohexyl; Trifluormethyl, Trichlormethyl, Trifluorethyl, Trifluormethoxymethyl.Halogencycloalkyl, each with 1 to 9 fluorine, chlorine and / or bromine atoms. R 7 and R 8 , together with the nitrogen atom to which they are attached, preferably form a saturated heterocycle having 5 to 8 ring atoms, which is optionally monosubstituted to tetrasubstituted, identically or differently, by halogen or CQ-alkyl, the heterocycle 1 or can contain 2 further, non-adjacent heteroatoms from the series oxygen, sulfur or NR 12 . R 7 and R 8 independently of one another particularly preferably represent hydrogen, methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, cyclopropyl, cyclopentyl, cyclohexyl ; Trifluoromethyl, trichloromethyl, trifluoroethyl, trifluoromethoxymethyl.
R7 und R8 bilden außerdem gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, besonders bevorzugt einen gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Fluor,R 7 and R 8 , together with the nitrogen atom to which they are attached, particularly preferably form one optionally up to four times, identical or different by fluorine,
Chlor, Brom oder Methyl substituierten gesättigten Heterocyclus aus der Reihe Morpholin, Thiomorpholin oder Piperazin, wobei das Piperazin am zweiten Stickstoffatom durch R12 substituiert sein kann.Chlorine, bromine or methyl substituted saturated heterocycle from the series morpholine, thiomorpholine or piperazine, where the piperazine on the second nitrogen atom can be substituted by R 12 .
R9 und R10 stehen unabhängig voneinander bevorzugt für Wasserstoff, Cι-C6-Alkyl, C3-C6-Cycloal- yl; C C4-Halogenalkyl, C3-C6-Halogencycloalkyl mit jeweils 1 bis 9 Fluor-, Chlor- und/oder Bromatomen. R9 und R10 bilden außerdem gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, bevorzugt einen gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Halogen oder Cr R 9 and R 10 independently of one another are preferably hydrogen, -CC 6 -alkyl, C 3 -C 6 -cycloal- yl; CC 4 haloalkyl, C 3 -C 6 halocycloalkyl each having 1 to 9 fluorine, chlorine and / or bromine atoms. R 9 and R 10 , together with the nitrogen atom to which they are attached, preferably form one optionally one or more times, identically or differently, by halogen or C r
C -Alkyl substituierten gesättigten Heterocyclus mit 5 bis 8 Ringatomen, wobei der Heterocyclus 1 oder 2 weitere, nicht benachbarte Heteroatome aus der Reihe Sauerstoff, Schwefel oder NR12 enthalten kann. R9 und R10 stehen unabhängig voneinander besonders bevorzugt für Wasserstoff, Methyl, Ethyl, n- oder iso-Propyl, n-, iso-, sec- oder tert-Butyl, Methoxymethyl, Methoxyethyl, Ethoxymethyl,C-alkyl substituted saturated heterocycle with 5 to 8 ring atoms, where the heterocycle can contain 1 or 2 further, non-adjacent heteroatoms from the series oxygen, sulfur or NR 12 . R 9 and R 10 independently of one another particularly preferably represent hydrogen, methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl, methoxymethyl, methoxyethyl, ethoxymethyl,
Ethoxyethyl, Cyclopropyl, Cyclopentyl, Cyclohexyl; Trifluormethyl, Trichlormethyl, Trifluorethyl, Trifluormethoxymethyl. R9 und R10 bilden außerdem gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, besonders bevorzugt einen gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Fluor, Chlor, Brom oder Methyl substituierten gesättigten Heterocyclus aus der Reihe Morpholin, Thiomo holin oder Piperazin, wobei das Piperazin am zweiten Stickstoffatom durch R12 substituiert sein kann.Ethoxyethyl, cyclopropyl, cyclopentyl, cyclohexyl; Trifluoromethyl, trichloromethyl, trifluoroethyl, trifluoromethoxymethyl. R 9 and R 10 , together with the nitrogen atom to which they are attached, particularly preferably form a saturated heterocycle from the series morpholine which may be mono- to tetrasubstituted, identically or differently, by fluorine, chlorine, bromine or methyl, Thiomo holin or piperazine, where the piperazine on the second nitrogen atom can be substituted by R 12 .
R11 steht bevorzugt für Wasserstoff, C C6-Alkyl, CrC4-Alkoxy, C,-C3-Alkoxy-CrC3-alkyl, C3- C6-Cycloalkyl; C C4-Halogenalkyl, C C4-Halogenalkoxy, Halogen-C C3-alkoxy-CrC3- alkyl, C3-C6-Halogencycloalkyl mit jeweils 1 bis 9 Fluor-, Chlor- und/oder Bromatomen. Rπ steht besonders bevorzugt für Wasserstoff, Methyl, Ethyl, n- oder iso-Propyl, tert-Butyl,R 11 preferably represents hydrogen, CC 6 -alkyl, C r C 4 -alkoxy, C, -C 3 -alkoxy-C r C 3 -alkyl, C 3 - C 6 -cycloalkyl; CC 4 haloalkyl, CC 4 -haloalkoxy, halo-C C 3 alkoxy-C r C 3 - alkyl, C 3 -C 6 -halocycloalkyl having in each case 1 to 9 fluorine, chlorine and / or bromine atoms. R π particularly preferably represents hydrogen, methyl, ethyl, n- or isopropyl, tert-butyl,
Methoxy, Ethoxy, iso-Propoxy, tert-Butoxy, Cyclopropyl; Trifluormethyl, Trifluormethoxy.Methoxy, ethoxy, iso-propoxy, tert-butoxy, cyclopropyl; Trifluoromethyl, trifluoromethoxy.
R12 steht bevorzugt für Wasserstoff oder C C4-Alkyl.R 12 preferably represents hydrogen or CC 4 alkyl.
R12 steht besonders bevorzugt für Wasserstoff, Methyl, Ethyl, n- oder iso-Propyl, n-, iso-, sec- oder tert-Butyl.R 12 particularly preferably represents hydrogen, methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl.
Z steht bevorzugt für Z1. Z1 steht bevorzugt für gegebenenfalls einfach bis fünffach, gleich oder verschieden substituiertes Phenyl, wobei die Substituenten aus der Liste W1 ausgewählt sind. Z1 steht besonders bevorzugt für einfach substituiertes Phenyl, wobei die Substituenten aus derZ preferably represents Z 1 . Z 1 preferably represents phenyl which is monosubstituted to pentas, identical or differently substituted, the substituents being selected from the list W 1 . Z 1 particularly preferably represents monosubstituted phenyl, where the substituents from
Liste W1 ausgewählt sind. Z1 steht auch besonders bevorzugt für zweifach, gleich oder verschieden substituiertes Phenyl, wobei die Substituenten aus der Liste W1 ausgewählt sind.List W 1 are selected. Z 1 also particularly preferably represents phenyl which is substituted twice, identically or differently, the substituents being selected from the list W 1 .
Z1 steht auch besonders bevorzugt für dreifach, gleich oder verschieden substituiertes Phenyl, wobei die Substituenten aus der Liste W1 ausgewählt sind. Z1 steht ganz besonders bevorzugt für einfach in 4-Position substituiertes Phenyl, wobei dieZ 1 also particularly preferably represents triple, identical or differently substituted phenyl, the substituents being selected from the list W 1 . Z 1 very particularly preferably represents phenyl which is monosubstituted in the 4-position, the
Substituenten aus der Liste W1 ausgewählt sind. Z1 steht ganz besonders bevorzugt für zweifach, gleich oder verschieden in 3,4-Position substituiertes Phenyl, wobei die Substituenten aus der Liste W1 ausgewählt sind. Z1 steht ganz besonders bevorzugt für zweifach, gleich oder verschieden in 2,4-Position substituiertes Phenyl, wobei die Substituenten aus der Liste W1 ausgewählt sind. Z1 steht ganz besonders bevorzugt für zweifach, gleich oder verschieden in 3,5-Position substituiertes Phenyl, wobei die Substituenten aus der Liste W1 ausgewählt sind.Substituents are selected from the list W 1 . Z 1 very particularly preferably represents phenyl which is substituted twice, identically or differently in the 3,4-position, the substituents being selected from the list W 1 . Z 1 very particularly preferably represents phenyl which is substituted twice, identically or differently in the 2,4-position, the substituents being selected from the list W 1 . Z 1 very particularly preferably represents phenyl which is substituted twice, identically or differently in the 3,5-position, the substituents being selected from the list W 1 .
Z1 steht ganz besonders bevorzugt für dreifach, gleich oder verschieden in 2,4,6-Position substituiertes Phenyl, wobei die Substituenten aus der Liste W1 ausgewählt sind.Z 1 very particularly preferably represents phenyl which is substituted three times, identically or differently in the 2,4,6-position, the substituents being selected from the list W 1 .
W1 steht für Halogen, Cyano, Nitro, A ino, Hydroxy, Formyl, Carboxyl, Carbamoyl, Thiocarb- amoyl; jeweils geradkettiges oder verzweigtes Alkyl, Hydroxyalkyl, Oxoalkyl, Alkoxy,W 1 stands for halogen, cyano, nitro, amino, hydroxy, formyl, carboxyl, carbamoyl, thiocarbamoyl; in each case straight-chain or branched alkyl, hydroxyalkyl, oxoalkyl, alkoxy,
Alkoxyalkyl, Alkylthioalkyl, Dialkoxyalkyl, Alkylthio, Alkylsulfinyl oder Alkylsulfonyl mit jeweils 1 bis 8 Kohlenstoffatomen; jeweils geradkettiges oder verzweigtes Alkenyl oder Alkenyloxy mit jeweils 2 bis 6 Kohlen- stoffatomen; jeweils geradkettiges oder verzweigtes Halogenalkyl, Halogenalkoxy, Halogenalkylthio,Alkoxyalkyl, alkylthioalkyl, dialkoxyalkyl, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 8 carbon atoms; each straight-chain or branched alkenyl or alkenyloxy each having 2 to 6 carbon atoms; each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio,
Halogenalkylsulfinyl oder Halogenalkylsulfonyl mit jeweils 1 bis 6 Kohlenstoffatomen und 1 bis 13 gleichen oder verschiedenen Halogenatomen; jeweils geradkettiges oder verzweigtes Halogenalkenyl oder Halogenalkenyloxy mit jeweils 2 bis 6 Kohlenstoffatomen und 1 bis 11 gleichen oder verschiedenen Halogenatomen; jeweils geradkettiges oder verzweigtes Alkylamino, Dialkylamino, Alkylcarbonyl, Alkyl- carbonyloxy, Alkoxycarbonyl, Alkylaminocarbonyl, Dialkylaminocarbonyl, Arylalkyl- aminocarbonyl, Dial ylaminocarbonyloxy mit 1 bis 6 Kohlenstoffatomen in den jeweiligen Kohlenwasserstoffketten, Alkenylcarbonyl oder Alkinylcarbonyl, mit 2 bis 6 Kohlenstoff- atomen in den jeweiligen Kohlenwasserstoffketten;Haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms; each straight-chain or branched haloalkenyl or haloalkenyloxy each having 2 to 6 carbon atoms and 1 to 11 identical or different halogen atoms; each straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, arylalkylaminocarbonyl, dial ylaminocarbonyloxy with 1 to 6 carbon atoms in the respective hydrocarbon chains, alkenylcarbonyl or alkynylcarbonyl, with 2 to 6 carbon atoms hydrocarbon chains;
Cycloalkyl oder Cycloalkyloxy mit jeweils 3 bis 6 Kohlenstoffatomen; jeweils gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Fluor, Chlor, Oxo, Methyl, Trifluormethyl oder Ethyl substituiertes, jeweils zweifach verknüpftes Alkylen mit 3 oder 4 Kohlenstoffatomen, Oxyal ylen mit 2 oder 3 Kohlenstoffatomen oder Dioxyalkylen mit 1 oder 2 Kohlenstoffatomen; oder eine Gruppierung -C(Q1)=N-Q2, worinCycloalkyl or cycloalkyloxy each having 3 to 6 carbon atoms; each optionally monosubstituted to tetrasubstituted, identically or differently, by fluorine, chlorine, oxo, methyl, trifluoromethyl or ethyl and in each case doubly linked alkylene having 3 or 4 carbon atoms, oxyalkylene having 2 or 3 carbon atoms or dioxyalkylene having 1 or 2 carbon atoms; or a grouping -C (Q 1 ) = NQ 2 , wherein
Q1 für Wasserstoff, Hydroxy, Alkyl mit 1 bis 4 Kohlenstoffatomen, Halogenalkyl mit 1 bis 4 Kohlenstoffatomen und 1 bis 9 gleichen oder verschiedenen Halogenatomen oder Cycloalkyl mit 1 bis 6 Kohlenstoffatomen steht und Q2 für Hydroxy, A ino, Methylamino, Phenyl, Benzyl oder für jeweils gegebenenfalls durch Halogen, Cyano, Hydroxy, Alkoxy, Alkylthio, Alkylamino, Dialkylamino oder Phenyl substituiertes Alkyl oder Alkoxy mit 1 bis 4 Kohlenstoffatomen, oder für Alkenyloxy oder Alkinyloxy mit jeweils 2 bis 4 Kohlenstoffatomen steht, sowie jeweils gegebenenfalls im Ringteil einfach bis dreifach durch Halogen, und/oder geradkettiges oder verzweigtes Alkyl oder Alkoxy mit 1 bis 4 Kohlenstoffatomen substituiertes Phenyl, Phenoxy, Phenyllthio, Benzoyl, Benzoylethenyl, Cinnamoyl, Heterocyclyl oder Phenylalkyl, Phenylalkyloxy, Phenylalkylthio, oder Heterocyclylalkyl, mit jeweils 1 bis 3 Kohlenstoffatomen in den jeweiligen Alkylteilen. steht bevorzugt für Fluor, Chlor, Brom, Methyl, Ethyl, n- oder iso-Propyl, n-, iso-, sec- oder tert-Butyl, Methoxy, Ethoxy, n- oder iso-Propoxy, Trifluormethyl, Trifluorethyl, Difluor- methoxy, Trifluormethoxy, Difluorchlormethoxy, Trifluorethoxy, jeweils zweifach ver- knüpftes Difluormethylendioxy oder Tetrafluorethylendioxy, oder eine Gruppierung -C(Q1)=N-Q2, worinQ 1 represents hydrogen, hydroxyl, alkyl having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms or cycloalkyl having 1 to 6 carbon atoms and Q 2 is hydroxyl, amino, methylamino, phenyl, benzyl or for alkyl or alkoxy with 1 to 4 carbon atoms, each optionally substituted by halogen, cyano, hydroxy, alkoxy, alkylthio, alkylamino, dialkylamino or phenyl, or for alkenyloxy or alkynyloxy each with 2 to 4 carbon atoms, and in each case optionally in the ring part simply to phenyl, phenoxy, phenyllthio, benzoyl, benzoylethenyl, cinnamoyl, heterocyclyl or phenylalkyl, phenylalkyloxy, phenylalkylthio, or heterocyclylalkyl, each having 1 to 3 carbon atoms, in each case substituted three times by halogen, and / or straight-chain or branched alkyl or alkoxy having 1 to 4 carbon atoms respective alkyl parts. preferably represents fluorine, chlorine, bromine, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, methoxy, ethoxy, n- or iso-propoxy, trifluoromethyl, trifluoroethyl, difluoro- methoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, each linked difluoromethylene dioxy or tetrafluoroethylene dioxy, or a group -C (Q 1 ) = NQ 2 , wherein
Q1 für Wasserstoff, Methyl, Ethyl, Trifluormethyl oder Cyclopropyl steht undQ 1 represents hydrogen, methyl, ethyl, trifluoromethyl or cyclopropyl and
Q2 für Hydroxy, Methoxy, Ethoxy, Propoxy oder Isopropoxy steht.Q 2 represents hydroxy, methoxy, ethoxy, propoxy or isopropoxy.
Z steht auch bevorzugt für Z2.Z also preferably represents Z 2 .
Z2 steht bevorzugt für gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Cι-C4-Z 2 preferably represents optionally up to four times, identical or different, by C 1 -C 4 -
Alkyl substituiertes Cycloalkyl oder Bicycloalkyl mit jeweils 3 bis 10 Kohlenstoffatomen. Z2 steht besonders bevorzugt für Cyclopentyl, Cyclohexyl, Cycloheptyl, Cyclooctyl, Cyclononyl, Bicyclo[2.2. l]heptyl oder Bicyclo[2.2.2]octyl.Alkyl substituted cycloalkyl or bicycloalkyl, each with 3 to 10 carbon atoms. Z 2 particularly preferably represents cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, bicyclo [2.2. l] heptyl or bicyclo [2.2.2] octyl.
Z steht auch bevorzugt für Z3.Z also preferably represents Z 3 .
Z3 steht bevorzugt für unsubstituiertes C2-C20-Alkyl oder für einfach oder mehrfach, gleich oder verschieden durch Fluor, Chlor, Brom, Iod und/oder C3-C6-Cycloalkyl substituiertes Cι-C20- Alkyl steht, wobei der Cycloalkylteil seinerseits gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Fluor, Chlor, Brom, Iod, C C4-Alkyl und/oder C C4-Halogenalkyl substituiert sein kann.Z 3 preferably stands for unsubstituted C 2 -C 20 alkyl or for mono- or polysubstituted, identically or differently, by fluorine, chlorine, bromine, iodine and / or C 3 -C 6 cycloalkyl-substituted -CC 20 alkyl, where the cycloalkyl part, in turn, may optionally be substituted up to four times, identically or differently, by fluorine, chlorine, bromine, iodine, CC 4 alkyl and / or CC 4 haloalkyl.
Z3 steht besonders bevorzugt für unsubstituiertes C2-C20-Alkyl.Z 3 particularly preferably represents unsubstituted C 2 -C 20 -alkyl.
Z3 steht auch besonders bevorzugt für durch Chlor, Cyclopropyl, Dichlorcyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl substituiertes d-do-Alkyl.Z 3 also particularly preferably represents d-do-alkyl substituted by chlorine, cyclopropyl, dichlorocyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Z steht auch bevorzugt für Z4.Z also preferably represents Z 4 .
Z4 steht bevorzugt für jeweils gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Fluor, Chlor, Brom, Iod und/oder C3-C6-Cycloalkyl substituiertes C2-C20-Alkenyl oder C2-C20-Alkinyl steht, wobei der Cycloalkylteil seinerseits gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Fluor, Chlor, Brom, Iod, C C4-Alkyl und/oder CZ 4 preferably represents C 2 -C 20 alkenyl or C 2 -C 20 alkynyl which is optionally substituted once or several times, identically or differently, by fluorine, chlorine, bromine, iodine and / or C 3 -C 6 cycloalkyl, the cycloalkyl part in turn optionally up to four times, identical or different by fluorine, chlorine, bromine, iodine, CC 4 alkyl and / or C
C4-Halogenalkyl substituiert sein kann. Z4 steht besonders bevorzugt für C2-C20-Alkenyl oder C2-C 0-Alkinyl.C 4 haloalkyl may be substituted. Z 4 particularly preferably represents C 2 -C 20 alkenyl or C 2 -C 0 alkynyl.
Z und R4 stehen auch bevorzugt gemeinsam mit den Kohlenstoffatomen, an die sie gebunden sind, für einen gegebenenfalls einfach bis vierfach, gleich oder verschieden substituierten 5- oderZ and R 4 are also preferably, together with the carbon atoms to which they are attached, an optionally mono- to tetrasubstituted, identical or differently substituted 5- or
6-gliedrigen carbocyclischen oder heterocyclischen Ring.6-membered carbocyclic or heterocyclic ring.
Z und R4 stehen auch besonders bevorzugt gememsam mit den Kohlenstoffatomen, an die sie gebunden sind, für einen gegebenenfalls einfach, zweifach oder dreifach durch Methyl substituierten 5- oder 6-gliedrigen carbocyclischen Ring. Bevorzugt sind außerdem Verbindungen der Formel (Ic)Z and R 4 are also particularly preferably, together with the carbon atoms to which they are attached, an optionally mono-, di- or trisubstituted by methyl-substituted 5- or 6-membered carbocyclic ring. Compounds of the formula (Ic) are also preferred
in welcher R1, R2, R3, R4 und Z1 die oben angegebenen Bedeutungen haben. Bevorzugt sind außerdem Verbindungen der Formel (Id) in which R 1 , R 2 , R 3 , R 4 and Z 1 have the meanings given above. Compounds of the formula (Id) are also preferred
in welcher R1, R2, R3, R4 und Z2 die oben angegebenen Bedeutungen haben. Bevorzugt sind außerdem Verbindungen der Formel (Ie) in which R 1 , R 2 , R 3 , R 4 and Z 2 have the meanings given above. Compounds of the formula (Ie) are also preferred
in welcher R1, R2, R3, R4 und Z3 die oben angegebenen Bedeutungen haben. Bevorzugt sind außerdem Verbindungen der Formel (If) in which R 1 , R 2 , R 3 , R 4 and Z 3 have the meanings given above. Compounds of the formula (If) are also preferred
in welcher R1, R2, R3, R4 und Z4 die oben angegebenen Bedeutungen haben. Bevorzugt sind außerdem Verbindungen der Formel (Ib) in which R 1 , R 2 , R 3 , R 4 and Z 4 have the meanings given above. Compounds of the formula (Ib) are also preferred
in welcher R , R , R , R und Z die oben angegebenen Bedeutungen haben. Bevorzugt sind außerdem Verbindungen der Formel (Ig) in which R, R, R, R and Z have the meanings given above. Compounds of the formula (Ig) are also preferred
in welcher R1, R2, R3, R4, R5"1 und Z die oben angegebenen Bedeutungen haben. in which R 1 , R 2 , R 3 , R 4 , R 5 "1 and Z have the meanings given above.
R5"1 steht bevorzugt für C C6-Alkyl, d-C4-Alkylsulfinyl, d-C4-Alkylsulfonyl, CrC3-Alkoxy- d-C3-alkyl, C3-C6-Cycloalkyl; Cι-C4-Halogenalkyl, C C4-Halogenalkylthio, C C4- Halogenalkylsulfmyl, C C4-Halogenalkylsulfonyl, Halogen-d-d-alkoxy-Crd-alkyl, C3- C6-Halogencycloalkyl mit jeweils 1 bis 9 Fluor-, Chlor- und/oder Bromatomen, Formyl-d- d-alkyl, (Cι-C3-Alkyl)carbonyl-d-C3-alkyl, (C C3-Alkoxy)carbonyl-CrC3-alkyl; (C C3- Halogenalkyl)carbonyl-C C3-alkyl, (Cι-C3-Halogenalkoxy)carbonyl-CrC3-alkyl mit jeweilsR 5 "1 preferably represents CC 6 -alkyl, dC 4 -alkylsulfinyl, dC 4 -alkylsulfonyl, C r C 3 -alkoxy-dC 3 -alkyl, C 3 -C 6 -cycloalkyl; Cι-C 4 -haloalkyl, CC 4 -haloalkylthio, CC 4 - haloalkylsulfmyl, CC 4 -haloalkylsulfonyl, halo-dd-alkoxy-Crd-alkyl, C 3 - C 6 -halo-cycloalkyl, each with 1 to 9 fluorine, chlorine and / or bromine atoms, formyl-d- d-alkyl, (-C-C 3 alkyl) carbonyl-dC 3 -alkyl, (CC 3 -alkoxy) carbonyl-C r C 3 -alkyl; (CC 3 - haloalkyl) carbonyl-C C 3 -alkyl, (Cι -C 3 haloalkoxy) carbonyl-C r C 3 alkyl with each
1 bis 7 Fluor-, Chlor- und/oder Bromatomen, (C C3-Alkyl)carbonyl-CrC3-halogenalkyl, (C C3-Alkoxy)carbonyl-Cι-C3-halogenalkyl mit jeweils 1 bis 6 Fluor-, Chlor- und/oder Bromatomen, (d-C3-Halogenalkyl)carbonyl-Cι-C3-halogenalkyl, (C C3-Halogenalkoxy)- carbonyl-C C3-halogenalkyl mit jeweils 1 bis 13 Fluor-, Chlor- und/oder Bromatomen; -COR6, -CONR7R8 oder -CH2NR9R10.1 to 7 fluorine, chlorine and / or bromine atoms, (CC 3 -alkyl) carbonyl-C r C 3 -haloalkyl, (CC 3 -alkoxy) carbonyl-Cι-C 3 -haloalkyl each with 1 to 6 fluorine, Chlorine and / or bromine atoms, (dC 3 -haloalkyl) carbonyl -CC-C 3 -haloalkyl, (CC 3 -haloalkoxy) - carbonyl-C C 3 -haloalkyl, each with 1 to 13 fluorine, chlorine and / or bromine atoms ; -COR 6 , -CONR 7 R 8 or -CH 2 NR 9 R 10 .
R5"1 steht besonders bevorzugt für Methyl, Ethyl, n- oder iso-Propyl, n-, iso-, sec- oder tert-Butyl, Pentyl oder Hexyl, Methylsulfmyl, Ethylsulfmyl, n- oder iso-Propylsulfmyl, n-, iso-, sec- oder tert-Butylsulfinyl, Methylsulfonyl, Ethylsulfonyl, n- oder iso-Propylsulfonyl, n-, iso-, sec- oder tert-Butylsulfonyl, Methoxymethyl, Methoxyethyl, Ethoxymethyl, Ethoxyethyl, Cyclopropyl, Cyclopentyl, Cyclohexyl, Trifluormethyl, Trichlormethyl, Trifluorethyl,R 5 "1 particularly preferably represents methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl, pentyl or hexyl, methylsulfmyl, ethylsulfmyl, n- or iso-propylsulfmyl, n-, iso-, sec- or tert-butylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or iso-propylsulfonyl, n-, iso-, sec- or tert-butylsulfonyl, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, cyclopropyl, cyclopentyl, cyclohexyl, trifluoromethyl, Trichloromethyl, trifluoroethyl,
Difluormethylthio, Difluorchlormethylthio, Trifluormethylthio, Trifluormethylsulfinyl, Trifluormethylsulfonyl, Trifluormethoxymethyl, -CH2-CHO, -CH2CH2-CHO, -CH2-CO-CH3, -CH2-CO-CH2CH3, -CH2-CO-CH(CH3)2, -CH2CH2-CO-CH3, -CH2CH2-CO-CH2CH3, -CH2CH2-CO-CH(CH3)2, -CH2-C(0)OCH3, -CH2-C(0)OCH2CH3, -CH2-C(0)OCH(CH3)2, -CH2CH2-C(0)OCH3, -CH2CH2-C(0)OCH2CH3, -CH2CH2-C(0)OCH(CH3)2, -CH2-CO-CF3,Difluoromethylthio, difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, trifluoromethoxymethyl, -CH 2 -CHO, -CH 2 CH 2 -CHO, -CH 2 -CO-CH 3 , -CH 2 -CO-CH 2 CH 3 , -CH 2 - CO-CH (CH 3 ) 2 , -CH 2 CH 2 -CO-CH 3 , -CH 2 CH 2 -CO-CH 2 CH 3 , -CH 2 CH 2 -CO-CH (CH 3 ) 2 , -CH 2 -C (0) OCH 3 , -CH 2 -C (0) OCH 2 CH 3 , -CH 2 -C (0) OCH (CH 3 ) 2 , -CH 2 CH 2 -C (0) OCH 3 , -CH 2 CH 2 -C (0) OCH 2 CH 3 , -CH 2 CH 2 -C (0) OCH (CH 3 ) 2 , -CH 2 -CO-CF 3 ,
-CH2-C0-CC13, -CH2-CO-CH2CF3, -CH2-CO-CH2CCl3, -CH2CH2-CO-CH2CF3, -CH2CH2-C0-CH2CC13, -CH2-C(0)OCH2CF3, -CH2-C(0)OCF2CF3, -CH2-C(0)0CH2CC13, -CH2-C(0)0CC12CC13, -CH2CH2-C(0)OCH2CF3, -CH2CH2-C(0)OCF2CF3,-CH 2 -C0-CC1 3 , -CH 2 -CO-CH 2 CF 3 , -CH 2 -CO-CH 2 CCl 3 , -CH 2 CH 2 -CO-CH 2 CF 3 , -CH 2 CH 2 - C0-CH 2 CC1 3 , -CH 2 -C (0) OCH 2 CF 3 , -CH 2 -C (0) OCF 2 CF 3 , -CH 2 -C (0) 0CH 2 CC1 3 , -CH 2 - C (0) 0CC1 2 CC1 3 , -CH 2 CH 2 -C (0) OCH 2 CF 3 , -CH 2 CH 2 -C (0) OCF 2 CF 3 ,
-CH2CH2-C(0)0CH2CC13, -CH2CH2-C(0)0-CC12CC13; -COR6, -CONR7R8 oder -CHzNRV.-CH 2 CH 2 -C (0) 0CH 2 CC1 3 , -CH 2 CH 2 -C (0) 0-CC1 2 CC1 3 ; -COR 6 , -CONR 7 R 8 or -CHzNRV.
R5"1 steht ganz besonders bevorzugt für Methyl, Methoxymethyl, -CH2-CHO, -CH2CH2-CHO, -CH2-CO-CH3, -CH2-CO-CH2CH3, -CH2-CO-CH(CH3)2 oder -COR6. Gesättigte oder ungesättigte Kohlenwasserstoffreste wie Alkyl oder Alkenyl können, auch inR 5 "1 very particularly preferably represents methyl, methoxymethyl, -CH 2 -CHO, -CH 2 CH 2 -CHO, -CH 2 -CO-CH 3 , -CH 2 -CO-CH 2 CH 3 , -CH 2 -CO-CH (CH 3 ) 2 or -COR 6 . Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl can also be used in
Verbindung mit Heteroatomen, wie z.B. in Alkoxy, soweit möglich, jeweils geradkettig oder verzweigt sein.Connection with heteroatoms, e.g. in alkoxy, where possible, be straight-chain or branched.
Die Definition CrC20-Alkyl umfasst den größten hierin definierten Bereich für einen Alkylrest. Im Einzelnen umfasst diese Definition die Bedeutungen Methyl, Ethyl, n-, iso-Propyl, n-, iso-, sec-, tert- Butyl, sowie jeweils alle isomeren Pentyle, Hexyle, Heptyle, Octyle, Nonyle, Decyle, Undecyle, Dodecyle, Tridecyle, Tetradecyle, Pentadecyle, Hexadecyle, Heptadecyle, Octadecyle, Nonadecyle und Eicosyle. Hierunter bevorzugt sind die Bedeutungen Methyl, Ethyl, n-, iso-Propyl, n-, iso-, sec-, tert-Butyl, n-Pentyl, 1-Methylbutyl, 2-Methylbutyl, 3-Methylbutyl, 1,2-Dimethylρropyl, 2,2-Dime- thylpropyl, n-Hexyl, 1-Methylpentyl, 4-Methylpentyl, 1,3-Dimethylbutyl, 3,3-Dimethylbutyl, 1,2,2- Trimethylpropyl, n-Heptyl, 1-Methylhexyl, 5-Methylhexyl, 1,4-Dimethylpentyl, 4,4-Dimethylpentyl, 1,3,3-Trimethylbutyl, 1,2,3-Trimethylbutyl.The definition C r C 20 alkyl encompasses the largest range defined here for an alkyl radical. Specifically, this definition includes the meanings methyl, ethyl, n-, iso-propyl, n-, iso-, sec-, tert-butyl, and all isomeric pentyls, hexyls, heptyls, octyls, nonyls, decyls, undecyls and dodecyls , Tridecyle, Tetradecyle, Pentadecyle, Hexadecyle, Heptadecyle, Octadecyle, Nonadecyle and Eicosyle. Preferred among these are the meanings methyl, ethyl, n-, isopropyl, n-, iso-, sec-, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylρropyl , 2,2-dimethylpropyl, n-hexyl, 1-methylpentyl, 4-methylpentyl, 1,3-dimethylbutyl, 3,3-dimethylbutyl, 1,2,2-trimethylpropyl, n-heptyl, 1-methylhexyl, 5th -Methylhexyl, 1,4-dimethylpentyl, 4,4-dimethylpentyl, 1,3,3-trimethylbutyl, 1,2,3-trimethylbutyl.
Die Definition C2-C20- Alkenyl umfasst den größten hierin definierten Bereich für einen Alkenylrest. Im Einzelnen umfasst diese Definition die Bedeutungen Ethenyl, 1-Propenyl, 2-Propenyl, iso- Propenyl, 1-Butenyl, 2-Butenyl, 3-Butenyl, 1 -Methyl- 1-propenyl, 2-Methyl-l-propenyl, l-Methyl-2- propenyl, 2-Methyl-2-propenyl, 1-Ethylethenyl, sowie jeweils alle isomeren Pentenyle, Hexenyle, Heptenyle, Octenyle, Nonenyle, Decenyle, Undecenyle, Dodecenyle, Tridecenyle, Tetradecenyle, Pentadecenyle, Hexadecenyle, Heptadecenyle, Octadecenyle, Nonadecenyle und Eicosenyle. Hierunter bevorzugt sind die Bedeutungen Ethenyl, 1-Propenyl, 2-Propenyl, 1-Butenyl, 2-Butenyl, 3- Butenyl, 1 -Methyl- 1-propenyl, 2-Methyl-l-propenyl, 1-Pentenyl, 4-Pentenyl, 1 -Methyl- 1-butenyl, 1,2-Dimethyl-l-propenyl, 1-Hexenyl, 5-Hexenyl, 1 -Methyl- 1-pentenyl, 1,3-Dimethyl-l-butenyl, 1- Methyl- 1 -hexenyl, 1,3,3 -Trimethyl- 1 -butenyl.The definition C 2 -C 20 alkenyl encompasses the largest range defined here for an alkenyl radical. Specifically, this definition includes the meanings ethenyl, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, l -Methyl-2-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, and in each case all isomeric pentenyls, hexenyls, heptenyls, octenyls, nonenyls, decenyls, undecenyls, dodecenyls, tridecenyls, tetradecenyls, pentadecenyls, hexadecenyls, heptadecenyls , Nonadecenyle and eicosenyle. Preferred meanings are ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-pentenyl, 4-pentenyl , 1-methyl-1-butenyl, 1,2-dimethyl-1-propenyl, 1-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1,3-dimethyl-1-butenyl, 1-methyl-1 -hexenyl, 1,3,3 -trimethyl-1-butenyl.
Die Definition C2-C20-Alkinyl umfasst den größten hierin definierten Bereich für einen Alkinylrest. Im Einzelnen umfasst diese Definition die Bedeutungen Ethinyl, 1-Propinyl, 2-Propinyl, 1-Butinyl, 2-Butinyl, 3-Butinyl, l-Methyl-2-propinyl, sowie jeweils alle isomeren Pentinyle, Hexinyle, Heptinyle, Octinyle, Noninyle, Decinyle, Undecinyle, Dodecinyle, Tridecinyle, Tetradecinyle, Pentadecinyle, Hexadecinyle, Heptadecinyle, Octadecinyle, Nonadecinyle und Eicosinyle. Hierunter bevorzugt sind die Bedeutungen Ethinyl, 1-Propinyl, 1-Butinyl, 3-Butinyl, l-Methyl-2-propinyl, 1- Pentinyl, 4-Pentinyl, 1-Hexinyl, 5-Hexinyl, 3,3-Dimethyl-l-butinyl, 4,4-Dimethyl-l-pentinyl, 4,4- Dimethyl-2-pentinyl, 1 ,4-Dimethyl-2-pentinyl.The definition C 2 -C 20 alkynyl encompasses the largest range defined here for an alkynyl radical. Specifically, this definition includes the meanings ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, l-methyl-2-propynyl, as well as all isomeric pentynyls, hexinyls, heptinyls, octynyls, noninyls , Decinyle, Undecinyle, Dodecinyle, Tridecinyle, Tetradecinyle, Pentadecinyle, Hexadecinyle, Heptadecinyle, Octadecinyle, Nonadecinyle and Eicosinyle. Preferred meanings are ethynyl, 1-propynyl, 1-butynyl, 3-butynyl, l-methyl-2-propynyl, 1-pentynyl, 4-pentynyl, 1-hexynyl, 5-hexynyl, 3,3-dimethyl-l -butinyl, 4,4-dimethyl-1-pentynyl, 4,4-dimethyl-2-pentynyl, 1,4-dimethyl-2-pentynyl.
Gegebenenfalls substituierte Reste können einfach oder mehrfach substituiert sein, wobei bei Mehrfachsubstitutionen die Substituenten gleich oder verschieden sein können. Durch Halogen substituierte Reste, wie z.B. Halogenalkyl, sind einfach oder mehrfach halogeniert. Bei mehrfacher Haloge ierung können die Halogenatome gleich oder verschieden sein. Halogen steht dabei für Fluor, Chlor, Brom und Iod, insbesondere für Fluor, Chlor und Brom.Optionally substituted radicals can be mono- or polysubstituted, and in the case of multiple substitutions the substituents can be the same or different. Residues substituted by halogen, such as haloalkyl, are halogenated once or more than once. In the case of multiple halogenation, the halogen atoms can be the same or different. Halogen stands for fluorine, chlorine, bromine and iodine, in particular for fluorine, chlorine and bromine.
Die oben aufgeführten allgemeinen oder in Vorzugsbereichen aufgeführten Restedefinitionen bzw. Erläuterungen können zwischen den jeweiligen Bereichen und Vorzugsbereichen beliebig kombiniert werden. Sie gelten für die Endprodukte sowie für die Vor- und Zwischenprodukte entsprechend.The general definitions or explanations of residues or explanations listed above or in preferred areas can be combined as desired between the respective areas and preferred areas. They apply accordingly to the end products as well as to the preliminary and intermediate products.
Erläuterungen der Verfahren und Zwischenprodukte:Explanations of the processes and intermediates:
Verfahren (a)Procedure (a)
Verwendet man 2-(Difluormethyl)benzoylchlorid und 4'-Chlor-3'-fluor-l, -biphenyl-2-amin als Ausgangsstoffe, so kann der Verlauf des erfindungsgemäßen Verfahrens (a) durch das folgende Formelschema veranschaulicht werden.If 2- (difluoromethyl) benzoyl chloride and 4'-chloro-3'-fluoro-l, -biphenyl-2-amine are used as starting materials, the course of process (a) according to the invention can be illustrated by the following formula.
Die zur Durchführung des erfindungsgemäßen Verfahrens (a) als Ausgangsstoffe benötigten Difluormethylbenzoyl-Derivate sind durch die Formel (II) allgemein definiert. In dieser Formel (II) steht X1 bevorzugt für Chlor oder Hydroxy.Formula (II) provides a general definition of the difluoromethylbenzoyl derivatives required as starting materials for carrying out process (a) according to the invention. In this formula (II), X 1 preferably represents chlorine or hydroxy.
Die Difluormethylbenzoyl-Derivate der Formel (II) sind neu. Sie werden erhalten, indem man j) 2-Formyl-benzonitril der Formel (XIV)The difluoromethylbenzoyl derivatives of the formula (II) are new. They are obtained by j) 2-formylbenzonitrile of the formula (XIV)
in einem ersten Schritt mit (Diethylamino)schwefeltrifluorid in Gegenwart eines Verdünnungsmittels (z.B. Methylenchlorid) fluoriert, und das so erhaltene 2-Difluormethyl-benzonitril der Formel (XV) fluorinated in a first step with (diethylamino) sulfur trifluoride in the presence of a diluent (for example methylene chloride), and the 2-difluoromethylbenzonitrile of the formula (XV) thus obtained
in einem zweiten Schritt mit einer Base (z.B. NaOH oder KOH) umsetzt [Verbindungen der reacted in a second step with a base (eg NaOH or KOH) [compounds of
Formel (II), in denen X1 für Hydroxy steht] und diese Säure in einem dritten Schritt gegebenenfalls mit einem Chlorierungsmittel (z.B.Formula (II) in which X 1 is hydroxy] and this acid in a third step, if appropriate with a chlorinating agent (for example
Thionylchlorid, Oxalylchlorid) in Gegenwart eines Verdünnungsmittels (z.B. Toluol, Methy- lenchlorid) zum entsprechenden Säurechlorid umsetzt [Verbindungen der Formel (II), in denen X1 für Chlor steht].Thionyl chloride, oxalyl chloride) in the presence of a diluent (for example toluene, methylene chloride) to give the corresponding acid chloride [compounds of the formula (II) in which X 1 is chlorine].
Die zur Durchführung des erfindungsgemäßen Verfahrens (a) weiterhin als Ausgangsstoffe benötigten Anilin-Derivate sind durch die Formel (HI) allgemein definiert. In dieser Formel (EU) haben R1, R2, R3, R4, R5 und Z bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt diejenigen Bedeutungen, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Verbindungen der Formel (I) als bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt für diese Reste angegeben wurden.Formula (HI) provides a general definition of the aniline derivatives which are further required as starting materials for carrying out process (a) according to the invention. In this formula (EU), R 1 , R 2 , R 3 , R 4 , R 5 and Z have preferred, particularly preferably or very particularly preferably, those meanings which have already been associated with the description of the compounds of the formula (I) according to the invention as preferred, particularly preferred or very particularly preferred for these radicals.
Die Ausgangsstoffe der Formel (III) sind größtenteils bekannt und/oder können nach bekannten Verfahren hergestellt werden (vgl. z.B. Bull. Korean Chem. Soc. 2000, 21, 165-166; Chem. Pharm. Bull. 1992, 40, 240-244; Heterocycles 1989, 29, 1013-1016; J. Med. Chem. 1996, 39, 892-903; Synthesis 1995, 713-16; Synth. Co mun. 1994, 24, 267-272; Synthesis 1994, 142-144; DE-A 2727416; DE-A 102 190 35; JP-A 9-132567; EP-A 0 824 099; WO 93/11117; EP-A 0 545 099; EP- A 0 589 301; EP-A 0 589 313 und WO 02/38542).Most of the starting materials of the formula (III) are known and / or can be prepared by known processes (cf. for example Bull. Korean Chem. Soc. 2000, 21, 165-166; Chem. Pharm. Bull. 1992, 40, 240- 244; Heterocycles 1989, 29, 1013-1016; J. Med. Chem. 1996, 39, 892-903; Synthesis 1995, 713-16; Synth. Co mun. 1994, 24, 267-272; Synthesis 1994, 142- 144; DE-A 2727416; DE-A 102 190 35; JP-A 9-132567; EP-A 0 824 099; WO 93/11117; EP-A 0 545 099; EP-A 0 589 301; EP-A 0 589 313 and WO 02/38542).
Es ist auch möglich zunächst Anilin-Derivate der Formel (HI), in welcher R5 für Wasserstoff steht, herzustellen und die so erhaltenen Verbindungen anschließend nach üblichen Methoden zu derivatisieren (z.B. analog zum erfindungsgemäßen Verfahren (i)).It is also possible first to prepare aniline derivatives of the formula (HI) in which R 5 is hydrogen and then to derivatize the compounds thus obtained by customary methods (for example analogously to process (i) according to the invention).
Verfahren (b)Method (b)
Verwendet man N-(2-Bromphenyl)-2-(difluormethyl)benzamid und 4-Chlor-3-fluorphenylboron- säure als Ausgangsstoffe sowie einen Katalysator, so kann der Verlauf des erfmdungsgemäßen Verfahrens (b) durch das folgende Formelschema veranschaulicht werden.If N- (2-bromophenyl) -2- (difluoromethyl) benzamide and 4-chloro-3-fluorophenylboronic acid are used as starting materials and a catalyst, the course of process (b) according to the invention can be illustrated by the following formula.
Die zur Durchführung des erfindungsgemäßen Verfahrens (b) als Ausgangsstoffe benötigten Halogen-difluormethylbenzanilide sind durch die Formel (TV) allgemein definiert. In dieser Formel (IV) haben R1, R2, R3, R4 und R5 bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt diejenigen Bedeutungen, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Verbindungen der Formel (I) als bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt für diese Reste angegeben wurden. X2 steht für Those required as starting materials for carrying out process (b) according to the invention Halogen-difluoromethylbenzanilides are generally defined by the formula (TV). In this formula (IV), R 1 , R 2 , R 3 , R 4 and R 5 have preferred, particularly preferably or very particularly preferably those meanings which have already been preferred in connection with the description of the compounds of the formula (I) according to the invention , particularly preferred or very particularly preferred for these radicals. X 2 stands for
Brom oder Iod.Bromine or iodine.
Die Halogen-difluormethylbenzanilide der Formel (TV) sind noch nicht bekannt. Sie sind als neue chemische Verbindungen ebenfalls Gegenstand der vorliegenden Anmeldung. Sie werden erhalten, indem man k) Difluormethylbenzoyl-Derivate der Formel (H)The halodifluoromethylbenzanilides of the formula (TV) are not yet known. As new chemical compounds, they are also the subject of the present application. They are obtained by k) difluoromethylbenzoyl derivatives of the formula (H)
in welcher X1 für Halogen oder Hydroxy steht, mit Halogenanilinen der Formel (XVI), in which X 1 represents halogen or hydroxy, with halogen anilines of the formula (XVI),
in welcher R , R , R , R , R und X2 die oben angegebenen Bedeutungen haben, gegebenenfalls in Gegenwart eines Katalysators, gegebenenfalls in Gegenwart eines Kondensationsmittels, gegebenenfalls in Gegenwart eines Säurebindemittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels, umsetzt. in which R, R, R, R, R and X 2 have the meanings given above, if appropriate in the presence of a catalyst, if appropriate in the presence of a condensing agent, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent.
Verfahren (k)Procedure (k)
Verwendet man 2-(Difluormethyl)benzoylchlorid und 2-Bromanüin als Ausgangsstoffe, so kann der Verlauf des erfindungsgemäßen Verfahrens (i) durch das folgende Formelschema veranschaulicht werden.If 2- (difluoromethyl) benzoyl chloride and 2-bromomanin are used as starting materials, the course of process (i) according to the invention can be illustrated by the following formula.
Die zur Durchführung des erfindungsgemäßen Verfahrens (k) als Ausgangsstoffe benötigten Difluormethylbenzoyl-Derivate der Formel (ET) sind bereits weiter oben im Zusammenhang mit dem erfindungsgemäßen Verfahren (a) beschrieben worden. The difluoromethylbenzoyl derivatives of the formula (ET) required as starting materials for carrying out the process (k) according to the invention are already further above in connection with the Process (a) according to the invention has been described.
Die zur Durchführung des erfindungsgemäßen Verfahrens (k) weiterhin als Ausgangsstoffe benötigten Halogenaniline sind durch die Formel (XVI) allgemein definiert. In dieser Formel (XVI) haben R1, R2, R3, R4, R5 und X2 bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt diejenigen Bedeutungen, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Verbindungen der Formel (I), bzw. die Vorprodukte der Formel (HI) als bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt für diese Reste angegeben wurden.Formula (XVI) provides a general definition of the halogen anilines which are further required as starting materials for carrying out process (k) according to the invention. In this formula (XVI), R 1 , R 2 , R 3 , R 4 , R 5 and X 2 have preferred, particularly preferably or very particularly preferably those meanings which have already occurred in connection with the description of the compounds of the formula (I ), or the precursors of the formula (HI) were given as preferred, particularly preferred or very particularly preferred for these radicals.
Die Halogenaniline der Formel (XVI) sind bekannte Synthesechemikalien oder können nach bekannten Verfahren erhalten werden. Im Fall, dass R5 nicht für Wasserstoff steht, kann der Rest R5 auf der Stufe der Verbindungen der Formel (XVI) durch übliche Derivatisierungsmethoden eingeführt werden. Es ist auch möglich, zunächst Verbindungen der Formel (TV), in denen R5 für Wasserstoff steht, herzustellen und die erhaltenen Produkte anschließend durch übliche Methoden zu derivatisieren (vgl. das erfindungsgemäße Verfahren (i)).The haloanilines of the formula (XVI) are known synthetic chemicals or can be obtained by known processes. In the event that R 5 is not hydrogen, the radical R 5 can be introduced at the level of the compounds of the formula (XVI) by customary derivatization methods. It is also possible first to prepare compounds of the formula (TV) in which R 5 is hydrogen and then to derivatize the products obtained by customary methods (cf. process (i) according to the invention).
Die zur Durchführung des erfindungsgemäßen Verfahrens (b) weiterhin als Ausgangsstoffe benötigten Boronsäure-Derivate sind durch die Formel (V) allgemein definiert. In dieser Formel (V) hat Z1 bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt diejenigen Bedeutungen, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Verbindungen der Formel (I) als bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt für Z1 angegeben wurden. A1 und A2 stehen jeweils für Wasserstoff oder zusammen für Tetramethylethylen.Formula (V) provides a general definition of the boronic acid derivatives which are further required as starting materials for carrying out process (b) according to the invention. In this formula (V), Z 1 has preferred, particularly preferred or very particularly preferred those meanings which have already been given as preferred, particularly preferred or very particularly preferred for Z 1 in connection with the description of the compounds of the formula (I) according to the invention were. A 1 and A 2 each represent hydrogen or together represent tetramethylethylene.
Die Boronsäure-Derivate der Formel (V) sind bekannt und/oder lassen sich nach bekannten Ver- fahren herstellen (vgl. z.B. WO 01/90084 und US 5,633,218).The boronic acid derivatives of the formula (V) are known and / or can be prepared by known processes (cf., for example, WO 01/90084 and US 5,633,218).
Verfahren (c)Procedure (c)
Verwendet man 2-{[2-(Difluormethyl)benzoyl]amino}phenylboronsäure und l-Brom-4-chlor-3- fluorbenzol als Ausgangsstoffe sowie einen Katalysator, so kann der Verlauf des erfindungsgemäßen Verfahrens (c) durch das folgende Formelschema veranschaulicht werden.If 2 - {[2- (difluoromethyl) benzoyl] amino} phenylboronic acid and l-bromo-4-chloro-3-fluorobenzene are used as starting materials and a catalyst, the course of process (c) according to the invention can be illustrated by the following formula ,
Die zur Durchführung des erfindungsgemäßen Verfahrens (c) als Ausgangsstoffe benötigten Those required as starting materials for carrying out process (c) according to the invention
Difluormethylbenzamid-Boronsäure-Derivate sind durch die Formel (VI) allgemein definiert. In dieser Formel (VI) haben R1, R2, R3, R4 und R5 bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt diejenigen Bedeutungen, die bereits im Zusammenhang mit der Beschreibung der er- findungsgemäßen Verbindungen der Formel (I) als bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt für diese Reste angegeben wurden. A3 und A4 stehen jeweils für Wasserstoff oder zusammen für Tetramethylethylen.Difluoromethylbenzamide boronic acid derivatives are generally defined by the formula (VI). In this formula (VI) R 1, R 2, R 3, R 4 and R 5 have preferred, particularly preferred and very particularly preferably have those meanings already mentioned in connection with the description of ER- inventive compounds of formula (I) as preferred, particularly preferred or very particularly preferred for these radicals. A 3 and A 4 each represent hydrogen or together represent tetramethylethylene.
Die Difluormethylbenzamid-Boronsäure-Derivate der Formel (VI) sind noch nicht bekannt. Sie sind neue chemische Verbindungen und ebenfalls Gegenstand der vorliegenden Anmeldung. Sie werden erhalten, indem man 1) Difluormethylbenzoyl-Derivate der Formel (H)The difluoromethylbenzamide-boronic acid derivatives of the formula (VI) are not yet known. They are new chemical compounds and are also the subject of the present application. They are obtained by 1) difluoromethylbenzoyl derivatives of the formula (H)
in welcher X1 für Halogen oder Hydroxy steht, mit Anilinboronsäurederivaten der Formel (XVH) in which X 1 represents halogen or hydroxy, with aniline boronic acid derivatives of the formula (XVH)
in welcher in which
R1, R2, R3, R4, R5, A3 und A4 die oben angegebenen Bedeutungen haben, gegebenenfalls in Gegenwart eines Katalysators, gegebenenfalls in Gegenwart eines Konden- sationsmittels, gegebenenfalls in Gegenwart eines Säurebindemittels und gegebenenfalls inR 1 , R 2 , R 3 , R 4 , R 5 , A 3 and A 4 have the meanings given above, if appropriate in the presence of a catalyst, if appropriate in the presence of a condensing agent, if appropriate in the presence of an acid binder and if appropriate in
Gegenwart eines Verdünnungsmittels, umsetzt.Presence of a diluent.
Verfahren (1)Process (1)
Verwendet man 2-(Difluormethyl)benzoylchlorid und 2-Aminophenylboronsäure als Ausgangsstoffe, so kann der Verlauf des erfindungsgemäßen Verfahrens (1) durch das folgende Formelschema veranschaulicht werden. If 2- (difluoromethyl) benzoyl chloride and 2-aminophenylboronic acid are used as starting materials, the course of process (1) according to the invention can be illustrated by the following formula.
Die zur Durchführung des erfindungsgemäßen Verfahrens (1) als Ausgangsstoffe benötigten Difluormethylbenzoyl-Derivate der Formel (H) sind bereits weiter oben im Zusammenhang mit dem erfindungsgemäßen Verfahren (a) beschrieben worden.The difluoromethylbenzoyl derivatives of the formula (H) required as starting materials for carrying out process (1) according to the invention have already been described above in connection with process (a) according to the invention.
Die weiterhin zur Durchführung des erfindungsgemäßen Verfahrens (1) als Ausgangsstoffe benötigten Anilinboronsäurederivate sind durch die Formel (XVπ) allgemein definiert. In dieser Formel (XVII) haben R1, R2, R3, R4 und R5 bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt diejenigen Bedeutungen, die bereits im Zusammenhang mit der Beschreibung der erfmdungsgemä- ßen Verbindungen der Formel (I) als bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt für diese Reste angegeben wurden. A3 und A4 stehen jeweils für Wasserstoff oder zusammen für Tetramethylethylen.Formula (XVπ) generally defines the aniline boronic acid derivatives which are further required as starting materials for carrying out process (1) according to the invention. In this formula (XVII), R 1 , R 2 , R 3 , R 4 and R 5 have preferred, particularly preferably or very particularly preferably, those meanings which have already occurred in connection with the description of the compounds of the formula (I) according to the invention as preferred, particularly preferred or very particularly preferred for these radicals. A 3 and A 4 each represent hydrogen or together represent tetramethylethylene.
Die Anilinboronsäurederivate der Formel (XVII) sind bekannte Synthesechemikalien oder können nach bekannten Verfahren erhalten werden. Im Fall, dass R5 nicht für Wasserstoff steht, kann der Rest R5 auf der Stufe der Verbindungen der Formel (XVH) durch übliche Derivatisierungsmethoden eingeführt werden. Es ist auch möglich, zunächst Verbindungen der Formel (VI), in denen R5 für Wasserstoff steht, herzustellen und die erhaltenen Produkte anschließend durch übliche Methoden zu derivatisieren (vgl. das erfindungsgemäße Verfahren (i)).The aniline boronic acid derivatives of the formula (XVII) are known synthetic chemicals or can be obtained by known processes. In the event that R 5 is not hydrogen, the radical R 5 can be introduced at the level of the compounds of the formula (XVH) by customary derivatization methods. It is also possible first to prepare compounds of the formula (VI) in which R 5 is hydrogen and then to derivatize the products obtained by customary methods (cf. process (i) according to the invention).
Die zur Durchführung des erfindungsgemäßen Verfahrens (c) weiterhin als Ausgangsstoffe benötigten Phenyl-Derivate sind durch die Formel (VII) allgemein definiert. In dieser Formel (VH) hat Z1 bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt diejenigen Bedeutungen, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Verbindungen der Formel (I) als bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt für Z1 angegeben wurden. X3 steht für Chlor, Brom, Iod oder Trifluormethylsulfonat.Formula (VII) provides a general definition of the phenyl derivatives which are furthermore required as starting materials for carrying out process (c) according to the invention. In this formula (VH), Z 1 has preferred, particularly preferred or very particularly preferred those meanings which have already been given as preferred, particularly preferred or very particularly preferred for Z 1 in connection with the description of the compounds of the formula (I) according to the invention were. X 3 stands for chlorine, bromine, iodine or trifluoromethyl sulfonate.
Die Phenyl-Derivate der Formel (VTT) sind bekannte Synthesechemikalien.The phenyl derivatives of the formula (VTT) are known synthetic chemicals.
Verfahren (d)Method (d)
Verwendet man N-(2-Bromphenyl)-2-(difluormethyl)benzamid und l-Brom-4-chlor-3-fluorbenzol als Ausgangsstoffe sowie einen Katalysator und 4,4,4',4',5,5,5',5'-Octamethyl-2,2,-bis-l,3,2-dioxa- borolan, so kann der Verlauf des erfindungsgemäßen Verfahrens (d) durch das folgende Formelschema veranschaulicht werden.If N- (2-bromophenyl) -2- (difluoromethyl) benzamide and l-bromo-4-chloro-3-fluorobenzene are used as starting materials and a catalyst and 4,4,4 ', 4', 5,5,5 ' , 5'-octamethyl-2,2 , -bis-l, 3,2-dioxa- borolan, the course of process (d) according to the invention can be illustrated by the following formula.
Die zur Durchführung des erfindungsgemäßen Verfahrens (d) als Ausgangsstoffe benötigten Halo- gen-difluormethylbenzanilide der Formel (IV), sowie die Phenyl-Derivate der Formel (VII) sind bereits weiter oben im Zusammenhang mit den erfindungsgemäßen Verfahren (b) und (c) beschrieben worden.The halogen-difluoromethylbenzanilides of the formula (IV) required as starting materials for carrying out the process (d) according to the invention, and the phenyl derivatives of the formula (VII) have already been mentioned above in connection with the processes (b) and (c) according to the invention have been described.
Das weiterhin zur Durchführung des erfindungsgemäßen Verfahrens (d) benötigte 4,4,4',4',5,5,5',5'- Octamethyl-2,2'-bis-l,3,2-dioxaborolan ist eine handelsübliche Synthesechemikalie.The 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bis-l, 3,2-dioxaborolane required to carry out process (d) according to the invention is commercially available chemical for synthesis.
Verfahren (e)Method (s)
Hydriert man beispielsweise 2-(Difluormethyl)-N-{2-(l,3-dimethyl-l-butenyl)phenyl}benzamid so kann der Verlauf des erfindungsgemäßen Verfahrens (e) durch das folgende Formelschema veran- schaulicht werden.If, for example, 2- (difluoromethyl) -N- {2- (1,3-dimethyl-l-butenyl) phenyl} benzamide is hydrogenated, the course of process (e) according to the invention can be illustrated by the following formula.
Die zur Durchführung des erfindungsgemäßen Verfahrens (e) als Ausgangsstoffe benötigten Difluormethylbenzanilide sind durch die Formel (Ia) allgemein definiert. In dieser Formel (Ia) haben R1, R2, R3, R4 und R5 bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt diejenigen Bedeutungen, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Verbindungen der Formel (I) als bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt für diese Reste angegeben wurden.Formula (Ia) provides a general definition of the difluoromethylbenzanilides required as starting materials for carrying out process (e) according to the invention. In this formula (Ia), R 1 , R 2 , R 3 , R 4 and R 5 have preferred, particularly preferably or very particularly preferably those meanings which have already been preferred in connection with the description of the compounds of the formula (I) according to the invention , particularly preferred or very particularly preferred for these radicals.
Die Verbindungen der Formel (Ia) sind erfindungsgemäße Verbindungen und können nach den Verfahren (a), (f), (g) oder (h) hergestellt werden. Verfahren (f)The compounds of the formula (Ia) are compounds according to the invention and can be prepared by processes (a), (f), (g) or (h). Method (f)
Dehydratisiert man beispielsweise 2-(Difluormethyl)-N-[2-(l-hydroxy-l,3-dimethylbutyl)phenyl]- benzamid, so kann der Verlauf des erfindungsgemäßen Verfahrens (f) durch das. folgende Formelschema veranschaulicht werden.If, for example, 2- (difluoromethyl) -N- [2- (l-hydroxy-1,3-dimethylbutyl) phenyl] benzamide is dehydrated, the course of process (f) according to the invention can be illustrated by the following formula.
Die zur Durchführung des erfindungsgemäßen Verfahrens (f) als Ausgangsstoffe benötigten Hydroxyalkyl-difluormethylbenzanilide sind durch die Formel (VHI) allgemein definiert. In dieser Formel (VIII) haben R1, R2, R3, R4 und R5 bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt diejenigen Bedeutungen, die bereits im Zusammenhang mit der Beschreibung der er- findungsgemäßen Verbindungen der Formel (I) als bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt für diese Reste angegeben wurden.Formula (VHI) provides a general definition of the hydroxyalkyl difluoromethylbenzanilides required as starting materials for carrying out process (f) according to the invention. In this formula (VIII) R 1, R 2, R 3, R 4 and R 5 have preferred, particularly preferred and very particularly preferably have those meanings already mentioned in connection with the description of ER- inventive compounds of formula (I) as preferred, particularly preferred or very particularly preferred for these radicals.
X5 steht bevorzugt für gegebenenfalls zusätzlich einfach bis vierfach, gleich oder verschieden durch Chlor, Fluor, Brom und/oder d-Q-Cycloalkyl substituiertes C2-C]2- Hydroxyalkyl, wobei der Cycloalkylteil seinerseits gegebenenfalls durch Halogen und/oder d-C4- Alkyl substituiert sein kann.X 5 preferably represents C 2 -C 2 -hydroxyalkyl which is optionally monosubstituted to tetrasubstituted, identically or differently, by chlorine, fluorine, bromine and / or dQ-cycloalkyl, the cycloalkyl part in turn optionally being halogen and / or dC 4 -alkyl can be substituted.
X5 steht besonders bevorzugt für gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Fluor, Cyclopropyl, Difluorcyclopropyl, Cyclobutyl, Cyclopentyl und/oder Cyclohexyl substituiertes, jeweils geradkettiges oder verzweigtes, jeweils an beliebiger Stelle verknüpftes Hydroxyethyl, Hydroxypropyl, Hydroxybutyl, Hydroxypentyl, Hydroxyhexyl,X 5 particularly preferably represents optionally up to four times, identically or differently, substituted by fluorine, cyclopropyl, difluorocyclopropyl, cyclobutyl, cyclopentyl and / or cyclohexyl, in each case straight-chain or branched, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl,
Hydroxyheptyl, Hydroxyoctyl, Hydroxynonyl oder Hydroxydecyl.Hydroxyheptyl, Hydroxyoctyl, Hydroxynonyl or Hydroxydecyl.
Die Verbindungen der Formel (VTH) sind noch nicht bekannt und als neue Verbindungen ebenfalls Gegenstand der vorliegenden Anmeldung.The compounds of the formula (VTH) are not yet known and are also the subject of the present application as new compounds.
Es wurde auch gefunden, dass die Hydroxyalkyl-difluormethylbenzanilide der Formel (VHI) sehr gute mikrobizide Eigenschaften besitzen und zur Bekämpfung unerwünschter Mikroorganismen sowohl im Pflanzenschutz als auch im Materialschutz eingesetzt werden können.It has also been found that the hydroxyalkyl difluoromethylbenzanilides of the formula (VHI) have very good microbicidal properties and can be used to control unwanted microorganisms both in crop protection and in material protection.
Die Hydroxyalkyl-difluormethylbenzanilide der Formel (VHI) werden erhalten, indem man m) Difluormethylbenzoyl-Derivate der Formel (H) in welcher X1 für Halogen oder Hydroxy steht, mit Hydroxyalkylanilinderivaten der Formel (XVHI)The hydroxyalkyl difluoromethylbenzanilides of the formula (VHI) are obtained by m) difluoromethylbenzoyl derivatives of the formula (H) in which X 1 represents halogen or hydroxy, with hydroxyalkylaniline derivatives of the formula (XVHI)
in welcher in which
R1, R2, R3, R4, R5 und X5 die oben angegebenen Bedeutungen haben, gegebenenfalls in Gegenwart eines Katalysators, gegebenenfalls in Gegenwart eines Kondensationsmittels, gegebenenfalls in Gegenwart eines Säurebindemittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels, umsetzt.R 1 , R 2 , R 3 , R 4 , R 5 and X 5 have the meanings given above, if appropriate in the presence of a catalyst, if appropriate in the presence of a condensing agent, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent.
Verfahren (m)Procedure (noun)
Verwendet man beispielsweise 2-(Difluormethyl)benzoylchlorid und 2-(2-Aminophenyl)-2-pentanol als Ausgangsstoffe, so kann der Verlauf des erfindungsgemäßen Verfahrens (m) durch das folgende Formelschema veranschaulicht werden:If, for example, 2- (difluoromethyl) benzoyl chloride and 2- (2-aminophenyl) -2-pentanol are used as starting materials, the course of the process (m) according to the invention can be illustrated by the following formula:
Die zur Durchführung des erfindungsgemäßen Verfahrens (m) als Ausgangsstoffe benötigten Difluormethylbenzoyl-Derivate der Formel (II) sind bereits weiter oben im Zusammenhang mit dem erfindungsgemäßen Verfahren (a) beschrieben worden.The difluoromethylbenzoyl derivatives of the formula (II) required as starting materials for carrying out process (m) according to the invention have already been described above in connection with process (a) according to the invention.
Die zur Durchführung des erfindungsgemäßen Verfahrens (1) als Ausgangsstoffe weiterhin benötigten Hydroxyalkylanilinderivate sind durch die Formel (XVHI) allgemein definiert. In dieser Formel (XVTH) haben R1, R2, R3, R4, R5 und X5 bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt diejenigen Bedeutungen, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Verbindungen der Formeln (I) bzw. (VHT) als bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt für diese Reste angegeben wurden. Die Hydroxyalkylanilinderivate der Formel (XVHI) sind bekannt und/oder können nach bekannten Methoden erhalten werden (vgl. z.B. US 3,917,592 oder EP-A 0 824099). Im Fall, dass R5 nicht für Wasserstoff steht, kann der Rest R5 auf der Stufe der Verbindungen der Formel (XVIII) durch übliche Derivatisierungsmethoden eingeführt werden. Es ist auch möglich, zunächst Verbindungen der Formel (VIH), in denen R5 für Wasserstoff steht, herzustellen und die erhaltenen Produkte anschließend durch übliche Methoden zu derivatisieren [vgl. das erfindungsgemäße Verfahren (i)].Formula (XVHI) provides a general definition of the hydroxyalkylaniline derivatives which are further required as starting materials for carrying out process (1) according to the invention. In this formula (XVTH), R 1 , R 2 , R 3 , R 4 , R 5 and X 5 have preferred, particularly preferably or very particularly preferably those meanings which have already been connected with the description of the compounds of the formulas (I ) or (VHT) as preferred, particularly preferred or very particularly preferred for these radicals. The hydroxyalkylaniline derivatives of the formula (XVHI) are known and / or can be obtained by known methods (cf., for example, US Pat. No. 3,917,592 or EP-A 0 824099). In the event that R 5 is not hydrogen, the radical R 5 can be introduced at the level of the compounds of the formula (XVIII) by customary derivatization methods. It is also possible to first prepare compounds of the formula (VIH) in which R 5 represents hydrogen and then to derivatize the products obtained by customary methods [cf. the inventive method (i)].
Verfahren (g)Process (g)
Verwendet man beispielsweise N-(2-Bromphenyl)-2-(difluormethyl)benzamid und 1 -Hexin als Ausgangsstoffe sowie einen Katalysator, so kann der Verlauf des erfindungsgemäßen Verfahrens (g) durch das folgende Formelschema veranschaulicht werden.If, for example, N- (2-bromophenyl) -2- (difluoromethyl) benzamide and 1-hexin are used as starting materials and a catalyst, the course of process (g) according to the invention can be illustrated by the following formula.
Die zur Durchführung des erfindungsgemäßen Verfahrens (g) als Ausgangsstoffe benötigten Halogen-difluormethylbenzanilide der Formel (TV) sind bereits weiter oben im Zusammenhang mit dem erfindungsgemäßen Verfahrens (c) beschrieben worden.The halodifluoromethylbenzanilides of the formula (TV) required as starting materials for carrying out process (g) according to the invention have already been described above in connection with process (c) according to the invention.
Die zur Durchführung des erfindungsgemäßen Verfahrens (g) weiterhin als Ausgangsstoffe benötigten Alkine sind durch die Formel (IX) allgemein definiert.Formula (IX) provides a general definition of the alkynes further required as starting materials for carrying out process (g) according to the invention.
steht bevorzugt für gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Fluor, Chlor, Brom und/oder C3-C6-Cycloalkyl substituiertes C2-Cι0-Alkyl, wobei der Cycloalkylteil seinerseits gegebenenfalls durch Halogen und/oder C C - Alkyl substituiert sein kann. steht besonders bevorzugt für gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Fluor, Cyclopropyl, Difluorcyclopropyl, Cyclobutyl, Cyclopentyl und/oder Cyclohexyl substituiertes, jeweils geradkettiges oder verzweigtes, jeweils an beliebiger Stelle verknüpftes Ethyl, Propyl, Butyl, Pentyl, Hexyl, Heptyl oder Octyl.preferably represents optionally mono- to tetrasubstituted by identical or different fluorine, chlorine, bromine and / or C 3 -C 6 cycloalkyl-substituted C 2 -Cι 0 alkyl, where the cycloalkyl moiety for its part is optionally substituted by halogen and / or CC - substituted alkyl can be. stands particularly preferably for optionally mono- to tetrasubstituted, identically or differently, fluorine, cyclopropyl, difluorocyclopropyl, cyclobutyl, cyclopentyl and / or cyclohexyl, in each case straight-chain or branched, in each case linked ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl.
Die Alkine der Formel (VI) sind bekannte Synthesechemikalien. Die zur Durchführung des erfindungsgemäßen Verfahrens (g) weiterhin alternativ als Ausgangsstoffe benötigten Alkene sind durch die Formel (X) allgemein definiert.The alkynes of the formula (VI) are known synthetic chemicals. Formula (X) provides a general definition of the alkenes which are alternatively required as starting materials for carrying out process (g) according to the invention.
A6, A7 und A8 stehen unabhängig voneinander bevorzugt jeweils für Wasserstoff oder gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Fluor, Chlor, Brom und/oder C3-C6-A 6 , A 7 and A 8 independently of one another preferably each represent hydrogen or, if appropriate, up to four times, identically or differently, by fluorine, chlorine, bromine and / or C 3 -C 6 -
Cycloalkyl substituiertes Alkyl, wobei der Cycloalkylteil seinerseits gegebenenfalls durchCycloalkyl substituted alkyl, the cycloalkyl part in turn optionally being replaced by
Halogen und/oder C]-C -Alkyl substituiert sein kann und die Gesamtzahl derHalogen and / or C] -C alkyl may be substituted and the total number of
Kohlenstoffatome des offenkettigen Molekülteils die Zahl 12 nicht übersteigt.Carbon atoms of the open-chain part of the molecule does not exceed the number 12.
A6, A7 und A8 stehen unabhängig voneinander besonders bevorzugt jeweils für Wasserstoff oder ge- gebenenfalls einfach bis vierfach, gleich oder verschieden durch Fluor, Cyclopropyl,A 6 , A 7 and A 8 independently of one another particularly preferably each represent hydrogen or, if appropriate, one to four times, identically or differently, by fluorine, cyclopropyl,
Difluorcyclopropyl, Cyclobutyl, Cyclopentyl und/ oder Cyclohexyl substituiertes, jeweils geradkettiges oder verzweigtes, jeweils an beliebiger Stelle verknüpftes Ethyl, Propyl, Butyl, Pentyl, Hexyl, Heptyl oder Ocryl, wobei die Gesamtzahl der Kohlenstoffatome des offenkettigen Molekülteils die Zahl 12 nicht übersteigt.Difluorocyclopropyl, cyclobutyl, cyclopentyl and / or cyclohexyl substituted, in each case straight-chain or branched, ethyl, propyl, butyl, pentyl, hexyl, heptyl or acrylic, each linked at any desired position, the total number of carbon atoms in the open-chain part of the molecule not exceeding 12.
Die Alkene der Formel (VH) sind bekannte Synthesechemikalien.The alkenes of the formula (VH) are known synthetic chemicals.
Verfahren (h)Procedure (h)
Verwendet man N-(2-Acetylphenyl)-2-(difluormethyl)benzamid und Butyl(triphenyl)-phosphonium- iodid als Ausgangsstoffe, so kann der Verlauf des erfindungsgemäßen Verfahrens (h) durch das folgende Formelschema veranschaulicht werden:If N- (2-acetylphenyl) -2- (difluoromethyl) benzamide and butyl (triphenyl) phosphonium iodide are used as starting materials, the course of process (h) according to the invention can be illustrated by the following formula:
Die zur Durchführung des erfindungsgemäßen Verfahrens (h) als Ausgangsstoffe benötigten Ketone sind durch die Formel (XI) allgemein definiert. In dieser Formel haben R1, R2, R3, R4 und R5 bevor- zugt, besonders bevorzugt bzw. ganz besonders bevorzugt diejenigen Bedeutungen, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Verbindungen der Formel (I) als bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt für diese Reste angegeben wurden.Formula (XI) provides a general definition of the ketones required as starting materials for carrying out process (h) according to the invention. In this formula, R 1 , R 2 , R 3 , R 4 and R 5 have preferred, particularly preferably or very particularly preferably, those meanings which have already been preferred in connection with the description of the compounds of the formula (I) according to the invention, were particularly preferred or very particularly preferred for these radicals.
A9 steht bevorzugt für gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Fluor, Chlor, Brom und oder C3-C6-Cycloalkyl substituiertes C2-Cι0- Alkyl, wobei der Cycloalkylteil seinerseits gegebenenfalls durch Halogen und/oder Cι-C4-Alkyl substituiert sein kann.A 9 preferably represents optionally mono- to tetrasubstituted by identical or different fluorine, chlorine, bromine and or C 3 -C 6 cycloalkyl-substituted C 2 -Cι 0 - alkyl, where the cycloalkyl moiety for its part is optionally substituted by halogen and / or Cι-C 4 alkyl may be substituted.
A9 steht besonders bevorzugt für gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Fluor, Cyclopropyl, Difluorcyclopropyl, Cyclobutyl, Cyclopentyl und/oder Cyclohexyl substituiertes, jeweils geradkettiges oder verzweigtes, jeweils an beliebiger Stelle verknüpftes Ethyl, Propyl, Butyl, Pentyl, Hexyl, Heptyl oder Octyl.A 9 particularly preferably represents optionally up to four times, identical or different from fluorine, cyclopropyl, difluorocyclopropyl, cyclobutyl, cyclopentyl and / or cyclohexyl Substituted, straight-chain or branched, in each case linked ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl.
Die Ketone der Formel (VHI) sind noch nicht bekannt. Sie sind als neue chemische Verbindungen ebenfalls Gegenstand der vorliegenden Anmeldung. Sie werden erhalten, indem man n) Difluormethylbenzoyl-Derivate der Formel (H)The ketones of the formula (VHI) are not yet known. As new chemical compounds, they are also the subject of the present application. They are obtained by n) difluoromethylbenzoyl derivatives of the formula (H)
in welcher X1 für Halogen oder Hydroxy steht, mit Ketoanilinen der Formel (XIX) in which X 1 represents halogen or hydroxy, with ketoanilines of the formula (XIX)
in welcher R1, R2, R3, R4, R5 und A9 die oben angegebenen Bedeutungen haben, gegebenenfalls in Gegenwart eines Katalysators, gegebenenfalls in Gegenwart eines Kondensationsmittels, gegebenenfalls in Gegenwart eines Säurebindemittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels, umsetzt. Verfahren (n) in which R 1 , R 2 , R 3 , R 4 , R 5 and A 9 have the meanings given above, if appropriate in the presence of a catalyst, if appropriate in the presence of a condensing agent, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent , Method (s)
Verwendet man 2-(Difluormethyl)benzoylchlorid und l-(2-Aminophenyl)ethanon als Ausgangsstoffe, so kann der Verlauf des erfindungsgemäßen Verfahrens (n) durch das folgende Formelschema veranschaulicht werden:If 2- (difluoromethyl) benzoyl chloride and 1- (2-aminophenyl) ethanone are used as starting materials, the course of the process (s) according to the invention can be illustrated by the following formula:
Die zur Durchführung des erfindungsgemäßen Verfahrens (n) als Ausgangsstoffe benötigten Difluormethylbenzoyl-Derivate der Formel (H) sind bereits weiter oben im Zusammenhang mit dem erfindungsgemäßen Verfahrens (a) beschrieben worden. Die zur Durchführung des erfindungsgemäßen Verfahrens (n) weiterhin als Ausgangsstoffe benötigten Ketoaniline sind durch die Formel (XIX) allgemein definiert. In dieser Formel (XIX) haben R1, R2, R3, R4, R5 und A9 bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt diejenigen Bedeutungen, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Verbindun- gen der Formeln (I) bzw. (XI) als bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt für diese Reste angegeben wurden.The difluoromethylbenzoyl derivatives of the formula (H) required as starting materials for carrying out process (s) according to the invention have already been described above in connection with process (a) according to the invention. Formula (XIX) provides a general definition of the ketoanilines which are further required as starting materials for carrying out process (s) according to the invention. In this formula (XIX), R 1, R 2, R 3, R 4, R 5 and A are 9 preferred, particularly preferred and very particularly preferred meanings, the gene already in connection with the description of the invention of formulas Verbindun- (I) or (XI) were given as preferred, particularly preferred or very particularly preferred for these radicals.
Die Ketoaniline der Formel (XIX) sind bekannt (vgl. J. Am. Chem. Soc. 1978, 100, 4842-4857 oder US 4,032,573) und/oder können nach bekannten Methoden erhalten werden. Im Fall, dass R5 nicht für Wasserstoff steht, kann der Rest R5 auf der Stufe der Verbindungen der Formel (XXII) durch übliche Derivatisierungsmethoden eingeführt werden. Es ist auch möglich, zunächst Verbindungen der Formel (VIII), in denen R5 für Wasserstoff steht, herzustellen und die erhaltenen Produkte anschließend durch übliche Methoden zu derivatisieren (vgl. das erfindungsgemäße Verfahren (i)).The ketoanilines of the formula (XIX) are known (cf. J. Am. Chem. Soc. 1978, 100, 4842-4857 or US 4,032,573) and / or can be obtained by known methods. In the event that R 5 is not hydrogen, the radical R 5 can be introduced at the level of the compounds of the formula (XXII) by customary derivatization methods. It is also possible first to prepare compounds of the formula (VIII) in which R 5 is hydrogen and then to derivatize the products obtained by customary methods (cf. process (i) according to the invention).
Die zur Durchführung des erfindungsgemäßen Verfahrens (h) weiterhin als Ausgangsstoffe benötigten Phosphorverbindungen sind durch die Formel (XII) allgemein definiert.Formula (XII) provides a general definition of the phosphorus compounds which are further required as starting materials for carrying out process (h) according to the invention.
A10 steht bevorzugt für gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Chlor, Fluor, Brom und/oder C3-C6-Cycloalkyl substituiertes C2-Cι0-Alkyl, wobei der Cycloalkylteil seinerseits gegebenenfalls durch Halogen und/oder Ci-Q-Alkyl substituiert sein kann.A 10 preferably represents optionally mono- to tetrasubstituted by identical or different substituents from chlorine, fluorine, bromine and / or C 3 -C 6 cycloalkyl-substituted C 2 -Cι 0 alkyl, where the cycloalkyl moiety for its part may be substituted by halogen and / or C Q-alkyl can be substituted.
A10 steht besonders bevorzugt für gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Fluor, Cyclopropyl, Difluorcyclopropyl, Cyclobutyl, Cyclopentyl und/oder Cyclohexyl substituiertes, jeweils geradkettiges oder verzweigtes, jeweils an beliebiger Stelle verknüpftes Ethyl, Propyl, Butyl, Pentyl, Hexyl, Heptyl oder Octyl. Px steht bevorzugt für eine Gruppierung -P^CeH^ Cl", -P+(C6H5)3 Br", -P+(C6H5)3 r, -P(=0)(OCH3)3 oder -P(=0)(OC2H5)3.A 10 particularly preferably represents optionally up to four times, identical or different, substituted by fluorine, cyclopropyl, difluorocyclopropyl, cyclobutyl, cyclopentyl and / or cyclohexyl, in each case straight-chain or branched, ethyl, propyl, butyl, pentyl, hexyl, linked at any point, Heptyl or octyl. Px preferably represents a group -P ^ CeH ^ Cl " , -P + (C6H 5 ) 3 Br " , -P + (C6H 5 ) 3 r, -P (= 0) (OCH 3 ) 3 or -P ( = 0) (OC 2 H 5 ) 3 .
Die Phosphorverbindungen der Formel (XU) sind bekannt und/oder können nach bekannten Verfahren hergestellt werden (vgl. Justus Liebigs Ann. Chem. 1953, 580, 44-57 oder Pure Appl. Chem. 1964, 9, 307-335).The phosphorus compounds of the formula (XU) are known and / or can be prepared by known processes (cf. Justus Liebigs Ann. Chem. 1953, 580, 44-57 or Pure Appl. Chem. 1964, 9, 307-335).
Verfahren (i)Procedure (i)
Verwendet man N-(4'-Chlor-3'-fluor-l,r-biphenyl-2-yl)-2-(difluormethyl)benzamid und Acetyl- chlorid als Ausgangsstoffe, so kann der Verlauf des erfindungsgemäßen Verfahrens (i) durch das folgende Formelschema veranschaulicht werden: If N- (4'-chloro-3'-fluoro-l, r-biphenyl-2-yl) -2- (difluoromethyl) benzamide and acetyl chloride are used as starting materials, the process (i) according to the invention can be followed by the following formula scheme can be illustrated:
Die zur Durchführung des erfindungsgemäßen Verfahrens (i) als Ausgangsstoffe benötigten Difluormethylbenzanilide sind durch die Formel (Ib) allgemein definiert. In dieser Formel (Ib) haben R1, R2, R3, R4 und Z bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt diejenigen Bedeutungen, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Verbindungen der Formel (I) als bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt für diese Reste angegeben wurden.Formula (Ib) provides a general definition of the difluoromethylbenzanilides required as starting materials for carrying out process (i) according to the invention. In this formula (Ib), R 1 , R 2 , R 3 , R 4 and Z have preferred, particularly preferably or very particularly preferably, those meanings which have already been preferred in connection with the description of the compounds of the formula (I) according to the invention, were particularly preferred or very particularly preferred for these radicals.
Die Verbindungen der Formel (Ib) sind erfindungsgemäße Verbindungen und können nach den Verfahren (a) bis (h) hergestellt werden.The compounds of the formula (Ib) are compounds according to the invention and can be prepared by processes (a) to (h).
Die zur Durchführung des erfindungsgemäßen Verfahrens (i) weiterhin als Ausgangsstoffe benötigten Halogenide sind durch die Formel (XTTT) allgemein definiert. In dieser Formel (XÜI) steht R5"1 bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt für diejenigen Bedeutungen, die bereits oben in Zusammenhang mit der Beschreibung der Verbindungen der Formel (Ig) als bevorzugt, besonders bevorzugt bzw. ganz besonders bevorzugt für diese Reste angegeben wurden. X6 steht für Chlor, Brom oder Iod.Formula (XTTT) provides a general definition of the halides required as starting materials for carrying out process (i) according to the invention. In this formula (XÜI), R 5 ″ 1 is preferably, particularly preferably or very particularly preferably for those meanings which are already preferred, particularly preferred or very particularly preferred in connection with the description of the compounds of the formula (Ig) these residues have been indicated X 6 represents chlorine, bromine or iodine.
Halogenide der Formel (XIII) sind bekannt.Halides of the formula (XIII) are known.
Reaktionsbedingungen > Reaction conditions >
Als Verdünnungsmittel zur Durchführung der erfindungsgemäßen Verfahren (a), (k), (1), (m) und (n) kommen alle inerten organischen Lösungsmittel in Betracht. Hierzu gehören vorzugsweise aliphati- sche, alicyclische oder aromatische Kohlenwasserstoffe, wie beispielsweise Petrolether, Hexan, Heptan, Cyclohexan, Methylcyclohexan, Benzol, Toluol, Xylol oder Decalin; halogenierte Kohlenwasserstoffe, wie beispielsweise Chlorbenzol, Dichlorbenzol, Dichlormethan, Chloroform, Tetrachlormethan, Dichlorethan oder Trichlorethan; Ether, wie Diethylether, Diisopropylether, Methyl- tert-butylether, Methyl-tert-Amylether, Dioxan, Tetrahydrofuran, 1,2-Dimethoxyethan, 1,2-Di- ethoxyethan oder Anisol; Ketone, wie Aceton, Butanon, Methyl-isobutylketon oder Cyclohexanon; Nitrile, wie Acetonitril, Propionitril, n- oder iso-Butyronitril oder Benzonitril; Amide, -wie N,N-Di- methylformamid, N,N-Dimethylacetamid, N-Methylformanilid, N-Methylpyrrolidon oder Hexame- thylphosphorsäuretriamid; deren Gemische mit Wasser oder reines Wasser.Suitable diluents for carrying out processes (a), (k), (1), (m) and (n) are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Ketones such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; Nitriles such as acetonitrile, propionitrile, n- or iso-butyronitrile or benzonitrile; Amides, -like N, N-Di- methylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; their mixtures with water or pure water.
Die erfindungsgemäßen Verfahren (a), (k), (1), (m) und (n) werden gegebenenfalls in Gegenwart eines geeigneten Säureakzeptors durchgeführt. Als solche kommen alle üblichen anorganischen oder organischen Basen infrage. Hierzu gehören vorzugsweise Erdalkalimetall- oder Alkalimetallhydride, -hydroxide, -amide, -alkoholate, -acetate, -carbonate oder -hydrogencarbonate, wie beispielsweise Natriumhydrid, Natriumamid, Lithiumdiisopropylamid, Narrium-methylat, Natrium-ethylat, Kalium- tert.-butylat, Natriumhydroxid, Kaliumhydroxid, Natriumacetat, Natriumcarbonat, Kaliumcarbonat, Kaliumhydrogencarbonat, Natriumhydrogencarbonat oder Ammoniumcarbonat, sowie tertiäre Amine, wie Trimethylamin, Triethylamin, Tributylamin, N,N-Dimethylanilin, N,N-Dimethyl-benzyl- amin, Pyridin, N-Methylpiperidin, N-Methylmorpholin, N,N-Dimethylaminopyridin, Diazabicyc- looctan (DABCO), Diazabicyclononen (DBN) oder Diazabicycloundecen (DBU).Processes (a), (k), (1), (m) and (n) according to the invention are optionally carried out in the presence of a suitable acid acceptor. All conventional inorganic or organic bases are suitable as such. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, lithium diisopropylamide, narrium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide , Potassium hydroxide, sodium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethyl-benzylamine, pyridine, N-methylpiperidine, N- Methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).
Die erfindungsgemäßen Verfahren (a), (k), (1), (m) und (n) werden gegebenenfalls in Gegenwart eines geeigneten Kondensationsmittels durchgeführt. Als solche kommen alle üblicherweise für derartige Amidierungsreaktionen verwendbaren Kondensationsmittel infrage. Beispielhaft genannt seien Säurehalogenidbildner wie Phosgen, Phosphortribromid, Phosphortrichlorid, Phosphorpenta- chlorid, Phosphoroxychlorid oder Thionylchlorid; Anhydridbildner wie Chlorameisensäureethylester, Chlorameisensäuremethylester, Chlorameisensäureisopropylester, Chlorameisensäureisobutylester oder Methansulfonylchlorid; Carbodiimide, wie N,N'-Dicyclohexylcarbodiimid (DCC) oder andere übliche Kondensationsmittel, wie Phosphorpentoxid, Polyphosphorsäure, N,N'-Carbonyldiimidazol, 2-Ethoxy-N-ethoxycarbonyl- 1 ,2-dihydrochinolin (EEDQ), Triphenylphosphin/Tetrachlorkohlenstoff oder Brom-tripyrrolidinophosphonium-hexafluorophosphat.Processes (a), (k), (1), (m) and (n) according to the invention are optionally carried out in the presence of a suitable condensing agent. As such, all condensation agents which can usually be used for such amidation reactions are suitable. Examples include acid halide formers such as phosgene, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride or thionyl chloride; Anhydride formers such as ethyl chloroformate, methyl chloroformate, isopropyl chloroformate, isobutyl chloroformate or methanesulfonyl chloride; Carbodiimides, such as N, N'-dicyclohexylcarbodiimide (DCC) or other customary condensing agents, such as phosphorus pentoxide, polyphosphoric acid, N, N'-carbonyldiimidazole, 2-ethoxy-N-ethoxycarbonyl-1, 2-dihydroquinoline (EEDQ), triphenylphosphine / tetrachloride bromo-tripyrrolidinophosphonium hexafluorophosphate.
Die erfindungsgemäßen Verfahren (a), (k), (1), (m) und (n) werden gegebenenfalls in Gegenwart eines Katalysators durchgeführt. Beispielsweise genannt seien 4-Dimethylaminopyridin, 1-Hydroxy- benzotriazol oder Dimethylformamid.Processes (a), (k), (1), (m) and (n) according to the invention are optionally carried out in the presence of a catalyst. Examples include 4-dimethylaminopyridine, 1-hydroxybenzotriazole or dimethylformamide.
Die Reaktionstemperaturen können bei der Durchführung der erfindungsgemäßen Verfahren (a), (k), (1), (m) und (n) in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen von 0°C bis 150°C, vorzugsweise bei Temperaturen von 0°C bis 80°C.The reaction temperatures can be varied within a substantial range when carrying out processes (a), (k), (1), (m) and (n). In general, temperatures from 0 ° C to 150 ° C, preferably at temperatures from 0 ° C to 80 ° C.
Zur Durchführung des erfindungsgemäßen Verfahrens (a) zur Herstellung der Verbindungen der Formel (I) setzt man pro Mol des Difluormethylbenzoyl-Derivats der Formel (H) im allgemeinen 0,8 bis 15 Mol, vorzugsweise 0,8 bis 8 Mol an Anilin-Derivat der Formel (HI) ein. Zur Durchführung des erfindungsgemäßen Verfahrens (j) zur Herstellung der Verbindungen derTo carry out process (a) according to the invention for the preparation of the compounds of the formula (I), 0.8 to 15 mol, preferably 0.8 to 8 mol, of aniline derivative are generally employed per mole of the difluoromethylbenzoyl derivative of the formula (H) of the formula (HI). To carry out process (j) according to the invention for the preparation of the compounds of
Formel (TV) setzt man pro Mol des Difluormethylbenzoyl-Derivats der Formel (TT) im allgemeinenFormula (TV) is generally used per mole of the difluoromethylbenzoyl derivative of the formula (TT)
0,8 bis 15 Mol, vorzugsweise 0,8 bis 8 Mol an Halogenaniline der Formel (XHI) ein.0.8 to 15 moles, preferably 0.8 to 8 moles of haloanilines of the formula (XHI).
Zur Durchführung des erfindungsgemäßen Verfahrens (k) zur Herstellung der Verbindungen der Formel (VI) setzt man pro Mol des Difluormethylbenzoyl-Derivats der Formel (II) im allgemeinen 0,8 bis 15 Mol, vorzugsweise 0,8 bis 8 Mol an Anilinboronsäurederivat der Formel (XIV) ein.To carry out process (k) according to the invention for the preparation of the compounds of the formula (VI), 0.8 to 15 mol, preferably 0.8 to 8 mol, of aniline boronic acid derivative of the formula are generally employed per mole of the difluoromethylbenzoyl derivative of the formula (II) (XIV) a.
Zur Durchführung des erfindungsgemäßen Verfahrens (1) zur Herstellung der Verbindungen der Formel (VHI) setzt man pro Mol des Difluormethylbenzoyl-Derivats der Formel (TT) im allgemeinen 0,8 bis 15 Mol, vorzugsweise 0,8 bis 8 Mol an Hydroxyalkylanilinderivat der Formel (XV) ein.To carry out process (1) according to the invention for the preparation of the compounds of the formula (VHI), generally 0.8 to 15 mol, preferably 0.8 to 8 mol, of hydroxyalkylaniline derivative of the formula are employed per mole of the difluoromethylbenzoyl derivative of the formula (TT) (XV) a.
Zur Durchführung des erfindungsgemäßen Verfahrens (m) zur Herstellung der Verbindungen der Formel (IX) setzt man pro Mol des Difluormethylbenzoyl-Derivats der Formel (TT) im allgemeinen 0,8 bis 15 Mol, vorzugsweise 0,8 bis 8 Mol an Ketoanilin der Formel (XVI) ein.To carry out process (m) according to the invention for the preparation of the compounds of the formula (IX), 0.8 to 15 mol, preferably 0.8 to 8 mol, of ketoaniline of the formula are generally employed per mole of the difluoromethylbenzoyl derivative of the formula (TT) (XVI) a.
Als Verdünnungsmittel zur Durchführung der erfindungsgemäßen Verfahren (b), (c) und (d) kommen alle inerten organischen Lösungsmittel in Betracht. Hierzu gehören vorzugsweise aliphatische, alicyclische oder aromatische Kohlenwasserstoffe, wie z.B. Petrolether, Hexan, Heptan, Cyclohexan, Methylcyclohexan, Benzol, Toluol, Xylol oder Decalin; Ether, wie Diethylether, Diisopropylether, Methyl-tert-butylether, Methyl-tert-Amylether, Dioxan, Tetrahydrofuran, 1,2-Dimethoxyethan, 1,2- Diethoxyethan oder Anisol; Nitrile, wie Acetonitril, Propionitril, n- oder iso-Butyronitril oder Benzonitril; Amide, wie N,N-Dimethylformamid, N,N-Dimethylacetamid, N-Methylformanilid, N-Methyl- pyrrolidon oder Hexamethylphosphorsäuretriamid; Ester wie Essigsäuremethylester oder Essigsäure- ethylester; Sulfoxide, wie Dimethylsulfoxid; Sulfone, wie Sulfolan; Alkohole, wie Methanol, Ethanol, n- oder iso-Propanol, n-, iso-, sec- oder tert-Butanol, Ethandiol, Propan-l,2-diol, Ethoxyethanol, Methoxyethanol, Diethylenglykolmonomethylether, Diethylenglykolmonoethylether, deren Gemische mit Wasser oder reines Wasser.Suitable diluents for carrying out processes (b), (c) and (d) are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, e.g. Petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; Ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Nitriles such as acetonitrile, propionitrile, n- or iso-butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Alcohols, such as methanol, ethanol, n- or iso-propanol, n-, iso-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.
Die Reaktionstemperaturen können bei der Durchführung der erfindungsgemäßen Verfahren (b), (c) und (d) in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen von 0°C bis 180°C, vorzugsweise bei Temperaturen von 20°C bis 150°C.The reaction temperatures can be varied within a substantial range when carrying out processes (b), (c) and (d) according to the invention. In general, temperatures from 0 ° C to 180 ° C, preferably at temperatures from 20 ° C to 150 ° C.
Die der erfindungsgemäßen Verfahren (b), (c) und (d) werden gegebenenfalls in Gegenwart eines ge- eigneten Säureakzeptors durchgeführt. Als solche kommen alle üblichen anorganischen oder organischen Basen infrage. Hierzu gehören vorzugsweise Erdalkalimetall- oder Alkalimetallhydride, -hydroxide, -amide, -alkoholate, -acetate, fluoride, phosphate, -carbonate oder -hydrogencarbonate, wie beispielsweise Natriumhydrid, Natriumamid, Lithiumdiisopropylamid, Natrium-methylat, Na- trium-ethylat, Kalium-tert.-butylat, Natriumhydroxid, Kaliumhydroxid, Natriumacetat, Natriumphosphat, Kaliumphosphat, Kaliurnfluorid, Cäsiumfluorid, Natriumcarbonat, Kaliumcarbonat, Kaliumhydrogencarbonat, Natriumhydrogencarbonat oder Cäsiumcarbonat, sowie tertiäre Amine, wie Trimethylamin, Triethylamin, Tributylamin, N,N-Dimethylanilin, N,N-Dimethyl-benzylamin, Pyridin, N-Methylpiperidin, N-Methylmorpholin, N,N-Dimethylaminopyridin, Diazabicyclooctan (DABCO), Diazabicyclononen (DBN) oder Diazabicycloundecen (DBU).The processes (b), (c) and (d) according to the invention are optionally carried out in the presence of a suitable acid acceptor. All conventional inorganic or organic bases are suitable as such. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, fluorides, phosphates, carbonates or hydrogen carbonates, such as sodium hydride, sodium amide, lithium diisopropyl amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide , Sodium acetate, sodium phosphate, potassium phosphate, potassium fluoride, cesium fluoride, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or cesium carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethyl-benzylamine, pyridine Methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).
Die der erfindungsgemäßen Verfahren (b), (c) und (d) werden in Gegenwart eines Katalysators, wie beispielsweise eines Palladiumsalzes oder -komplexes, durchgeführt. Hierzu kommen vorzugsweise Palladiumchlorid, Palladiumacetat, Tetrakis-(triphenylphosphin)-Palladium, Bis-(triphenylphosphin)- Palladiumdichlorid oder (l,l'-Bis(diphenylphosphino)ferrocenpalladium(π)chlorid) infrage.The processes (b), (c) and (d) according to the invention are carried out in the presence of a catalyst, such as, for example, a palladium salt or complex. Palladium chloride, palladium acetate, tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride or (l, l'-bis (diphenylphosphino) ferrocene palladium (π) chloride) are preferably suitable for this purpose.
Es kann auch ein Palladiumkomplex in der Reaktionsmischung erzeugt werden, wenn man ein Palladiumsalz und ein Komplexligand, wie z.B. Triethylphosphan, Tri-tert-butylphosphan, Tricyclo- hexylphosphan, 2-(Dicyclohexylphosphan)-biphenyl, 2-(Di-tert-butylphosphan)-biphenyl, 2-(Di- cyclohexylphosphan)-2'-(N,N-dimethylamino)-biphenyl, Triphenylphosphan, Tris-(o-Tolyl)-phos- phan, Natrium 3-(Diphenylphosphino)benzolsulfonat, Tris-2-(Methoxyphenyl)-phosphan, 2,2'-Bis- (diphenylphosphan)-l,l'-bmaphthyl, l,4-Bis-(diphenylphosphan)-butan, l,2-Bis-(diphenylphos- phan)-ethan, l,4-Bis-(dicyclohexylphosphan)-butan, l,2-Bis-(dicyclohexylphosphan)-ethan, 2-(Di- cyclohexylphosphan)-2'-(N,N-dimethylamino)-biphenyl, Bis(diphenylphosphino)ferrocen oder Tris- (2,4-tert-butylphenyl)-phosphit getrennt zur Reaktion zugibt.A palladium complex can also be generated in the reaction mixture if a palladium salt and a complex ligand, e.g. Triethylphosphane, tri-tert-butylphosphine, tricyclohexylphosphine, 2- (dicyclohexylphosphine) biphenyl, 2- (di-tert-butylphosphine) biphenyl, 2- (dicyclohexylphosphine) -2 '- (N, N-dimethylamino) -biphenyl, triphenylphosphine, tris (o-tolyl) phosphine, sodium 3- (diphenylphosphino) benzenesulfonate, tris-2- (methoxyphenyl) phosphine, 2,2'-bis (diphenylphosphine) -l, l ' -bmaphthyl, 1,4-bis (diphenylphosphane) butane, 1,2-bis (diphenylphosphane) ethane, 1,4-bis (dicyclohexylphosphine) butane, 1,2-bis (dicyclohexylphosphine) -ethane, 2- (dicyclohexylphosphine) -2 '- (N, N-dimethylamino) biphenyl, bis (diphenylphosphino) ferrocene or tris (2,4-tert-butylphenyl) phosphite are added separately to the reaction.
Zur Durchführung des erfindungsgemäßen Verfahrens (b) zur Herstellung der Verbindungen der Formel (I) setzt man pro Mol des Halogen-difluormethylbenzanilids der Formel (IV) im allgemeinen 1 bis 15 Mol, vorzugsweise 2 bis 8 Mol an Boronsäurederivat der Formel (V) ein.To carry out process (b) according to the invention for the preparation of the compounds of the formula (I), 1 to 15 mol, preferably 2 to 8 mol, of boronic acid derivative of the formula (V) are generally employed per mol of the halodifluoromethylbenzanilide of the formula (IV) ,
Zur Durchführung des erfindungsgemäßen Verfahrens (c) zur Herstellung der Verbindungen der Formel (I) setzt man pro Mol des Difluormethylbenzamid-Boronsäure-Derivats der Formel (VT) im allgemeinen 0,8 bis 15 Mol, vorzugsweise 0,8 bis 8 Mol an Phenyl-Derivat der Formel (VH) ein.To carry out process (c) according to the invention for the preparation of the compounds of the formula (I), 0.8 to 15 mol, preferably 0.8 to 8 mol, of phenyl are generally employed per mol of the difluoromethylbenzamide-boronic acid derivative of the formula (VT) Derivative of the formula (VH).
Zur Durchführung des erfindungsgemäßen Verfahrens (d) zur Herstellung der Verbindungen der Formel (I) setzt man pro Mol des Halogen-difluormethylbenzanilids der Formel (IV) im allgemeinen 0,8 bis 15 Mol, vorzugsweise 0,8 bis 8 Mol an Phenyl-Derivat der Formel (VH) und 0,8 bis 15 Mol, vorzugsweise 0,8 bis 8 Mol an 4,4,4',4l,5,5,5',5'-Octamethyl-2,2'-bis-l,3,2-dioxaborolan ein. Als Verdünnungsmittel zur Durchführung des erfindungsgemäßen Verfahrens (e) kommen alle inerten organischen Lösungsmittel in Betracht. Hierzu gehören vorzugsweise aliphatische oder alicycli- sche Kohlenwasserstoffe, wie beispielsweise Petrolether, Hexan, Heptan, Cyclohexan, Methylcyclohexan oder Decalin; Ether, wie Diethylether, Diisopropylether, Methyl-tert-butylether, Methyl-tert- Amylether, Dioxan, Tefrahydrofuran, 1,2- Dimethoxyethan oder 1,2-Diethoxyethan; Alkohole, wie Methanol, Ethanol, n- oder iso-Propanol, n-, iso-, sec- oder tert-Butanol, Ethandiol, Propan-l,2-diol, Ethoxyethanol, Methoxyethanol, Diethylenglykolmonomethylether, Diethylenglykolmonoethylether, deren Gemische mit Wasser oder reines Wasser.To carry out process (d) according to the invention for the preparation of the compounds of the formula (I), 0.8 to 15 mol, preferably 0.8 to 8 mol, of phenyl derivative are generally employed per mole of the halodifluoromethylbenzanilide of the formula (IV) of the formula (VH) and 0.8 to 15 mol, preferably 0.8 to 8 mol of 4,4,4 ', 4 l , 5,5,5', 5'-octamethyl-2,2'-bis- l, 3,2-dioxaborolane. Suitable diluents for carrying out process (e) according to the invention are all inert organic solvents. These preferably include aliphatic or alicyclic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane or decalin; Ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tefrahydrofuran, 1,2-dimethoxyethane or 1,2-diethoxyethane; Alcohols, such as methanol, ethanol, n- or iso-propanol, n-, iso-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.
Das erfindungsgemäße (e) Verfahren wird in Gegenwart eines Katalysators durchgeführt. Als solche kommen alle Katalysatoren infrage, die für Hydrierungen üblicherweise verwendet werden. Beispielhaft seien genannt: Raney-Nickel, Palladium oder Platin, gegebenenfalls auf einem Trägermaterial, wie beispielsweise Aktivkohle.The process (s) according to the invention is carried out in the presence of a catalyst. All catalysts which are usually used for hydrogenations are suitable as such. Examples include: Raney nickel, palladium or platinum, optionally on a carrier material, such as activated carbon.
Die Hydrierung im erfindungsgemäßen Verfahren (e) kann statt in Gegenwart von Wasserstoff in Kombination mit einem Katalysator auch in Anwesenheit von Triethylsilan durchgeführt werden.The hydrogenation in process (e) according to the invention can also be carried out in the presence of triethylsilane instead of in the presence of hydrogen in combination with a catalyst.
Die Reaktionstemperaturen können bei der Durchführung des erfindungsgemäßen Verfahrens (e) in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen von 0°C bis 150°C, vorzugsweise bei Temperaturen von 20°C bis 100°C.The reaction temperatures can be varied within a substantial range when carrying out process (e) according to the invention. In general, temperatures from 0 ° C to 150 ° C, preferably at temperatures from 20 ° C to 100 ° C.
Das erfindungsgemäße Verfahren (e) wird unter einem Wasserstoffdruck zwischen 0.5 and 200 bar, bevorzugt zwischen 2 und 50 bar, besonders bevorzugt zwischen 3 und 10 bar durchgeführt.Process (e) according to the invention is carried out under a hydrogen pressure between 0.5 and 200 bar, preferably between 2 and 50 bar, particularly preferably between 3 and 10 bar.
Als Verdünnungsmittel zur Durchführung des erfindungsgemäßen Verfahrens (f) kommen alle inerten organischen Lösungsmittel in Betracht. Hierzu gehören vorzugsweise aliphatische, alicycli- sche oder aromatische Kohlenwasserstoffe, wie beispielsweise Petrolether, Hexan, Heptan, Cyclohexan, Methylcyclohexan, Benzol, Toluol, Xylol oder Decalin; halogenierte Kohlenwasserstoffe, wie beispielsweise Chlorbenzol, Dichlorbenzol, Dichlormethan, Chloroform, Tetrachlormethan, Dichlor- ethan oder Trichlorethan; Ether, wie Diethylether, Diisopropylether, Methyl-tert-butylether, Methyl- tert- Amylether, Dioxan, Tetrahydrofuran, 1,2- Dimethoxyethan, 1,2-Diethoxyethan oder Anisol; Ketone, wie Aceton, Butanon, Methyl-isobutylketon oder Cyclohexanon; Nitrile, wie Acetonitril, Propionitril, n- oder iso-Butyronitril oder Benzonitril; Amide, wie N,N-Dimethylformamid, N,N- Dimethylacetamid, N-Methylformanilid, N-Methylpyrrolidon oder Hexamethylphosphorsäure- triamid; Ester wie Essigsäuremethylester oder Essigsäureethylester; Sulfoxide, wie Dimethylsulfoxid; Sulfone, wie Sulfolan; Alkohole, wie Methanol, Ethanol, n- oder iso-Propanol, n-, iso-, sec- oder tert-Butanol, Ethandiol, Propan-l,2-diol, Ethoxyethanol, Methoxyethanol, Diethylenglykolmo- nomethylether, Diethylenglykolmonoethylether, deren Gemische mit Wasser oder reines Wasser.Suitable diluents for carrying out process (f) according to the invention are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Ketones such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; Nitriles such as acetonitrile, propionitrile, n- or iso-butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Alcohols, such as methanol, ethanol, n- or iso-propanol, n-, iso-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.
Das erfmdungsgemäße Verfahren (f) wird gegebenenfalls in Gegenwart einer Säure durchgeführt. Als solche kommen alle anorganischen und organischen Protonen- wie auch Lewissäuren, sowie auch alle polymeren Säuren infrage. Hierzu gehören beispielsweise Chlorwasserstoff, Schwefelsäure, Phosphorsäure, Ameisensäure, Essigsäure, Trifluoressigsäure, Methansulfonsäure, Trifluormethan- sulfonsäure, Toluolsulfonsäure, Bortrifluorid (auch als Etherat), Bortribromid, Aluminiumtrichlorid, Titantetrachlorid, Tetrabutylorthotitanat, Zinkchlorid, Eisen-III-chlorid, Antimonpentachlorid, saure Ionenaustauscher, saure Tonerden und saures Kieselgel.Process (f) according to the invention is optionally carried out in the presence of an acid. All inorganic and organic protonic and Lewis acids, as well as all polymeric acids, are suitable as such. These include, for example, hydrogen chloride, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, toluenesulfonic acid, boron trifluoride (also as etherate), boron tribromide, aluminum trichloride, titanium tetrachloride, tetrabutyl orthide chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride, zinc chloride from zinc chloride, , acidic clays and acidic silica gel.
Die Reaktionstemperaturen können bei der Durchführung des erfindungsgemäßen Verfahrens (f) in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen von 0°C bis 150°C, vorzugsweise bei Temperaturen von 0°C bis 100°C.The reaction temperatures can be varied within a substantial range when carrying out process (f) according to the invention. In general, temperatures from 0 ° C to 150 ° C, preferably at temperatures from 0 ° C to 100 ° C.
Die erfindungsgemäßen Verfahren (f) und (e) können auch in einer Tandemreaktion („Eintopf- Reaktion") durchgeführt werden. Dazu wird eine Verbindung der Formel (VHI) gegebenenfalls in Gegenwart eines Verdünnungsmittels (geeignete Lösungsmittel wie für Verfahren (f)), gegebenenfalls in Gegenwart einer Säure (geeignete Säuren wie für Verfahren (f)) und in Anwesenheit von Triethylsilan umgesetzt.Processes (f) and (e) according to the invention can also be carried out in a tandem reaction (“one-pot reaction”). For this purpose, a compound of the formula (VHI) is optionally in the presence of a diluent (suitable solvents as for process (f)), optionally in the presence of an acid (suitable acids as for process (f)) and in the presence of triethylsilane.
Als Verdünnungsmittel zur Durchführung des erfindungsgemäßen Verfahrens (g) kommen alle inerten organischen Lösungsmittel in Betracht. Hierzu gehören vorzugsweise Nitrile, wie Acetonitril, Propionitril, n- oder iso-Butyronitril oder Benzonitril oder Amide, wie N,N-Dimethylformamid, N,N- Dimethylacetamid, N-Methylformanilid, N-Methylpyrrolidon oder Hexamethylphosphorsäure- triamid.Suitable diluents for carrying out process (g) according to the invention are all inert organic solvents. These preferably include nitriles, such as acetonitrile, propionitrile, n- or iso-butyronitrile or benzonitrile or amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide.
Das erfindungsgemäße Verfahren (g) wird gegebenenfalls in Gegenwart eines geeigneten Säureakzeptors durchgeführt. Als solche kommen alle üblichen anorganischen oder organischen Basen infrage. Hierzu gehören vorzugsweise Erdalkalimetall- oder Alkalimetallhydride, -hydroxide, -amide, -alkoholate, -acetate, -carbonate oder -hydrogencarbonate, wie beispielsweise Natriumhydrid, Natri- umamid, Natrium-methylat, Natrium-ethylat, Kalium-tert.-butylat, Natriumhydroxid, Kaliumhydroxid, Ammoniumhydroxid, Natriumacetat, Kaliumacetat, Calciumacetat, Ammoniumacetat, Natrium- carbonat, Kaliumcarbonat, Kaliumhydrogencarbonat, Natriumhydrogencarbonat oder Ammonium- carbonat, sowie tertiäre Amine, wie Trimethylamin, Triethylamin, Tributylamin, N,N-Dimethylani- lin, N,N-Dimethyl-benzylamin, Pyridin, N-Methylpiperidin, N-Methylmorpholin, N,N-Dimethylami- nopyridin, Diazabicyclooctan (DABCO), Diazabicyclononen (DBN) oder Diazabicycloundecen (DBU).Process (g) according to the invention is optionally carried out in the presence of a suitable acid acceptor. All conventional inorganic or organic bases are suitable as such. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide , Potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N- Dimethyl-benzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylami- nopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).
Das erfindungsgemäße Verfahren (g) wird in Gegenwart eines oder mehrerer Katalysatoren durchgeführt.Process (g) according to the invention is carried out in the presence of one or more catalysts.
Dazu eignen sich besonders Palladiumsalze oder -komplexe. Hierzu kommen vorzugsweise Palladiumchlorid, Palladiumacetat, Tetrakis-(triphenylphosphin)-Palladium oder Bis-(triphenylphosphin)- Palladiumdichlorid infrage. Es kann auch ein Palladiumkomplex in der Reaktionsmischung erzeugt werden, wenn man ein Palladiumsalz und ein Komplexligand getrennt zur Reaktion zugibt.Palladium salts or complexes are particularly suitable for this. Palladium chloride, palladium acetate, tetrakis (triphenylphosphine) palladium or bis (triphenylphosphine) palladium dichloride are preferred for this purpose. A palladium complex can also be generated in the reaction mixture if a palladium salt and a complex ligand are added separately to the reaction.
Als Liganden kommen vorzugsweise Organophosphorverbindungen infrage. Beispielhaft seien genannt: Triphenylphosphin, tri-o-Tolylphosphin, 2,2'-Bis(diphenylphosphino)-l, -binaphthyl, Di- cyclohexylphosphinebiphenyl, 1 ,4-Bis(diphenylphosphino)butan, Bisdiphenylphosphinoferrocen, Di(tert.-butylphosphino)biphenyl, Di(cyclohexylphosphino)biphenyl, 2-Dicyclohexylphosphino-2'- N,N-dimethylaminobiphenyl, Tricyclohexylphosphin, Ttri-tert.-butylphosphine. Es kann aber auch auf Liganden verzichtet werden.Organophosphorus compounds are preferred as ligands. Examples include: triphenylphosphine, tri-o-tolylphosphine, 2,2'-bis (diphenylphosphino) -l, -binaphthyl, dicyclohexylphosphine biphenyl, 1,4-bis (diphenylphosphino) butane, bisdiphenylphosphinoferrocene, di (tert-butylphosphino) biphenyl, di (cyclohexylphosphino) biphenyl, 2-dicyclohexylphosphino-2'-N, N-dimethylaminobiphenyl, tricyclohexylphosphine, ttri-tert-butylphosphine. However, ligands can also be dispensed with.
Das erfindungsgemäße Verfahren (g) wird ferner gegebenenfalls in Gegenwart eines weiteren Metallsalzes, wie Kupfersalzen, beispielsweise Kupfer-(I)-iodid durchgeführt.Process (g) according to the invention is also optionally carried out in the presence of a further metal salt, such as copper salts, for example copper (I) iodide.
Die Reaktionstemperaturen- können bei der Durchführung des erfindungsgemäßen Verfahrens (g) in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen von 20°C bis 180°C, vorzugsweise bei Temperaturen von 50°C bis 150°C.The reaction temperatures can be varied within a substantial range when carrying out process (g) according to the invention. In general, temperatures from 20 ° C to 180 ° C, preferably at temperatures from 50 ° C to 150 ° C.
Zur Durchführung des erfindungsgemäßen Verfahrens (g) zur Herstellung der Verbindungen der Formel (I) setzt man pro mol des Halogen-difluormethylbenzanilids der Formel (IV) im allgemeinen 1 bis 5 mol, vorzugsweise 1 bis 2 mol an Alkin der Formel (IX) oder Alken der Formel (X) ein.To carry out process (g) according to the invention for the preparation of the compounds of the formula (I), 1 to 5 mol, preferably 1 to 2 mol, of alkyne of the formula (IX) or Alkene of formula (X).
Als Verdünnungsmittel zur Durchführung des erfindungsgemäßen Verfahrens (h) kommen alle inerten organischen Lösungsmittel in Betracht. Hierzu gehören vorzugsweise aliphatische, alicycli- sche oder aromatische Kohlenwasserstoffe, wie beispielsweise Petrolether, Hexan, Heptan, Cyclohexan, Methylcyclohexan, Benzol, Toluol, Xylol oder Decalin; halogenierte Kohlenwasserstoffe, wie z.B. Chlorbenzol, Dichlorbenzol, Dichlormethan, Chloroform, Tetrachlormethan, Dichlorethan oder Trichlorethan; Ether, wie Diethylether, Diisopropylether, Methyl-tert-butylether, Methyl-tert-Amyl- ether, Dioxan, Tetrahydrofuran, 1,2- Dimethoxyethan, 1,2-Diethoxyethan oder Anisol; Nitrile, wie Acetonitril, Propionitril, n- oder iso-Butyronitril oder Benzonitril; Amide, wie N,N-Dimethylform- amid, N,N-Dimethylacetamid, N-Methylformanilid, N-Methylpyrrolidon oder Hexamethylphosphor- säuretriamid; Ester wie Essigsäuremethylester oder Essigsäureethylester; Sulfoxide, wie Dimethylsulfoxid; Sulfone, wie Sulfolan; Alkohole, wie Methanol, Ethanol, n- oder iso-Propanol, n-, iso-, sec- oder tert-Butanol, Ethandiol, Propan-l,2-diol, Ethoxyethanol, Methoxyethanol, Diethylenglykolmo- nomethylether, Diethylenglykolmonoethylether.Suitable diluents for carrying out process (h) according to the invention are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Nitriles, like Acetonitrile, propionitrile, n- or iso-butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Alcohols, such as methanol, ethanol, n- or iso-propanol, n-, iso-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether.
Das erfindungsgemäße Verfahren (h) wird gegebenenfalls in Gegenwart eines geeigneten Säureakzeptors durchgeführt. Als solche kommen alle üblichen starken Basen infrage. Hierzu gehören vor- zugsweise Erdalkalimetall- oder Alkalimetallhydride, -hydroxide, -amide, -alkoholate oder Alkalimetall-Kohlenwasserstoffverbindungen, wie beispielsweise Natriumhydrid, Natriumhydroxid, Kaliumhydroxid, Natriumamid, Litiumdiisopropylamid, Natrium-methylat, Natrium-ethylat, Kalium- tert-butylat, Methylitium, Phenyllitium oder Butyllitium.Process (h) according to the invention is optionally carried out in the presence of a suitable acid acceptor. As such, all the usual strong bases come into question. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates or alkali metal hydrocarbon compounds, such as, for example, sodium hydride, sodium hydroxide, potassium hydroxide, sodium amide, lithium diisopropylamide, sodium methylate, sodium ethylate, potassium tert-butoxide, methylitium , Phenyllitium or butyllitium.
Die Reaktionstemperaturen können bei der Durchführung des erfindungsgemäßen Verfahrens (h) in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen von -80°C bis 150°C, vorzugsweise bei Temperaturen von -30°C bis 80°C.The reaction temperatures can be varied within a substantial range when carrying out process (h) according to the invention. In general, temperatures from -80 ° C to 150 ° C, preferably at temperatures from -30 ° C to 80 ° C.
Zur Durchführung des erfindungsgemäßen Verfahrens (h) zur Herstellung der Verbindungen der Formel (I) setzt man pro mol des Ketons der Formel (XI) im allgemeinen 1 bis 5 mol, vorzugsweise 1 bis 2 mol an Phosphorverbindung der Formel (Xtl) ein.To carry out process (h) according to the invention for the preparation of the compounds of the formula (I), 1 to 5 mol, preferably 1 to 2 mol, of phosphorus compound of the formula (Xtl) are generally employed per mol of the ketone of the formula (XI).
Als Verdünnungsmittel zur Durchführung des erfindungsgemäßens Verfahrens (i) kommen alle inerten organischen Lösungsmittel in Betracht. Hierzu gehören vorzugsweise aliphatische, alicyclische oder aromatische Kohlenwasserstoffe, wie beispielsweise Petrolether, Hexan, Heptan, Cyclohexan, Methylcyclohexan, Benzol, Toluol, Xylol oder Decalin; halogenierte Kohlenwasserstoffe, wie beispielsweise Chlorbenzol, Dichlorbenzol, Dichlormethan, Chloroform, Tetrachlormethan, Dichlorethan oder Trichlorethan; Ether, wie Diethylether, Diisopropylether, Methyl-tert- butylether, Methyl-tert-Amylether, Dioxan, Tetrahydrofuran, 1,2- Dimethoxyethan, 1,2- Diethoxyethan oder Anisol oder Amide, wie N,N-Dimethylformamid, N,N-Dimethylacetamid, N- Methylformanilid, N-Methylpyrrolidon oder Hexamethylphosphorsäuretriamid.Suitable diluents for carrying out process (i) according to the invention are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole or amides, such as N, N-dimethylformamide, N, N- Dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide.
Das erfindungsgemäße Verfahren (i) wird in Gegenwart einer Base durchgeführt. Als solche kommen alle üblichen anorganischen oder organischen Basen infrage. Hierzu gehören vorzugsweise Erdalkalimetall- oder Alkalimetallhydride, -hydroxide, -amide, -alkoholate, -acetate, -carbonate oderProcess (i) according to the invention is carried out in the presence of a base. All conventional inorganic or organic bases are suitable as such. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or
-hydrogencarbonate, wie beispielsweise Natriumhydrid, Natriumamid, Natrium-methylat, Natrium- ethylat, Kalium-tert.-butylat, Natriumhydroxid, Kaliumhydroxid, Ammoniumhydroxid, Natrium- acetat, Kaliumacetat, Calciumacetat, Ammoniumacetat, Natriumcarbonat, Kaliumcarbonat, Kalium- hydrogencarbonat, Natriumhydrogencarbonat oder Caesiumcarbonat, sowie tertiäre Amine, wie Trimethylamin, Triethylamin, Tributylamin, N,N-Dimethylanilin, N,N-Dimethyl-benzylamin, Pyridin, N-Methylpiperidin, N-Methylmorpholin, N,N-Dimethylaminopyridin, Diazabicyclooctan (DABCO), Diazabicyclononen (DBN) oder Diazabicycloundecen (DBU).bicarbonates such as sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or cesium carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethyl-benzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecen (DBU).
Die Reaktionstemperaturen können bei der Durchführung des erfindungsgemäßen Verfahrens (i) in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen von 0°C bis 150°C, vorzugsweise bei Temperaturen von 20°C bis 110°C.The reaction temperatures can be varied within a substantial range when carrying out process (i) according to the invention. In general, temperatures from 0 ° C to 150 ° C, preferably at temperatures from 20 ° C to 110 ° C.
Zur Durchführung des erfindungsgemäßen Verfahrens (i) zur Herstellung der Verbindungen der Formel (I) setzt man pro Mol des Iodpyrazolylcarboxanilids der Formel (Ib) im allgemeinen 0,2 bis 5 Mol, vorzugsweise 0,5 bis 2 Mol an Halogenid der Formel (XTTT) ein.To carry out process (i) according to the invention for the preparation of the compounds of the formula (I), 0.2 to 5 mol, preferably 0.5 to 2 mol, of halide of the formula (XTTT) are generally employed per mole of the iodopyrazolylcarboxanilide of the formula (Ib) ) on.
Alle erfindungsgemäßen Verfahren werden im allgemeinen unter Normaldruck durchgeführt. Es ist jedoch auch möglich, unter erhöhtem oder vermindertem Druck - im allgemeinen zwischen 0,1 bar und 10 bar - zu arbeiten.All processes according to the invention are generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure - generally between 0.1 bar and 10 bar.
Die erfindungsgemäßen Stoffe weisen eine starke mikrobizide Wirkung auf und können zur Bekämpfimg von unerwünschten Mikroorganismen, wie Fungi und Bakterien, im Pflanzenschutz und im Materialschutz eingesetzt werden.The substances according to the invention have a strong microbicidal action and can be used to control unwanted microorganisms, such as fungi and bacteria, in crop protection and in material protection.
Fungizide lassen sich Pflanzenschutz zur Bekämpfung von Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes und Deuteromycetes einsetzen.Fungicides can be used to protect plants against Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
Bakterizide lassen sich im Pflanzenschutz zur Bekämpfung von Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae und Streptomycetaceae einsetzen.Bactericides can be used in crop protection to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
Beispielhaft aber nicht begrenzend seien einige Erreger von pilzlichen und bakteriellen Erkrankungen, die unter die oben aufgezählten Oberbegriffe fallen, genannt: Xanthomonas-Arten, wie beispielsweise Xanthomonas campestris pv. oryzae; Pseudomonas-Arten, wie beispielsweise Pseudomonas syringae pv. lachrymans; Erwinia- Arten, wie beispielsweise Erwinia amylovora; Pythium-Arten, wie beispielsweise Pythium ultimum;Some pathogens of fungal and bacterial diseases which come under the generic names listed above may be mentioned as examples, but not by way of limitation: Xanthomonas species, such as, for example, Xanthomonas campestris pv. Oryzae; Pseudomonas species, such as, for example, Pseudomonas syringae pv. Lachrymans; Erwinia species, such as, for example, Erwinia amylovora; Pythium species, such as, for example, Pythium ultimum;
Phytophthora-Arten, wie beispielsweise Phytophthora infestans; Pseudoperonospora-Arten, wie beispielsweise Pseudoperonospora humuli oderPhytophthora species, such as, for example, Phytophthora infestans; Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or
Pseudoperonospora cubensis;Pseudoperonospora cubensis;
Plasmopara-Arten, wie beispielsweise Plasmopara viticola;Plasmopara species, such as, for example, Plasmopara viticola;
Bremia- Arten, wie beispielsweise Bremia lactucae; Peronospora- Arten, wie beispielsweise Peronospora pisi oder P. brassicae;Bremia species, such as, for example, Bremia lactucae; Peronospora species, such as, for example, Peronospora pisi or P. brassicae;
Erysiphe-Arten, wie beispielsweise Erysiphe graminis;Erysiphe species, such as, for example, Erysiphe graminis;
Sphaerotheca- Arten, wie beispielsweise Sphaerotheca fuliginea;Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;
Podosphaera- Arten, wie beispielsweise Podosphaera leucotricha;Podosphaera species, such as, for example, Podosphaera leucotricha;
Venturia- Arten, wie beispielsweise Venturia inaequalis; Pyrenophora-Arten, wie beispielsweise Pyrenophora teres oder P. gramineaVenturia species, such as, for example, Venturia inaequalis; Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea
(Konidienform: Drechslera, Syn: Helminthosporium);(Conidial form: Drechslera, Syn: Helminthosporium);
Cochliobolus-Arten, wie beispielsweise Cochliobolus sativusCochliobolus species, such as, for example, Cochliobolus sativus
(Konidienform: Drechslera, Syn: Helminthosporium);(Conidial form: Drechslera, Syn: Helminthosporium);
Uromyces- Arten, wie beispielsweise Uromyces appendiculatus; Puccinia- Arten, wie beispielsweise Puccinia recondita;Uromyces species, such as, for example, Uromyces appendiculatus; Puccinia species, such as, for example, Puccinia recondita;
Sclerotinia- Arten, wie beispielsweise Sclerotinia sclerotiorum;Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;
Tilletia- Arten, wie beispielsweise Tilletia caries;Tilletia species, such as, for example, Tilletia caries;
Ustilago-Arten, wie beispielsweise Ustilago nuda oder Ustilago avenae;Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;
Pellicularia-Arten, wie beispielsweise Pellicularia sasakii; Pyricularia-Arten, wie beispielsweise Pyricularia oryzae;Pellicularia species, such as, for example, Pellicularia sasakii; Pyricularia species, such as, for example, Pyricularia oryzae;
Fusarium- Arten, wie beispielsweise Fusarium culmorum;Fusarium species, such as, for example, Fusarium culmorum;
Botrytis- Arten, wie beispielsweise Botrytis cinerea;Botrytis species, such as, for example, Botrytis cinerea;
Septoria- Arten, wie beispielsweise Septoria nodorum;Septoria species, such as, for example, Septoria nodorum;
Leptosphaeria- Arten, wie beispielsweise Leptosphaeria nodorum; Cercospora-Arten, wie beispielsweise Cercospora canescens;Leptosphaeria species, such as, for example, Leptosphaeria nodorum; Cercospora species, such as, for example, Cercospora canescens;
Alternaria-Arten, wie beispielsweise Alternaria brassicae;Alternaria species, such as, for example, Alternaria brassicae;
Pseudocercosporella-Arten, wie beispielsweise Pseudocercosporella herpotrichoides.Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.
Die erfindungsgemäßen Wirkstoffe weisen auch eine starke stärkende Wirkung in Pflanzen auf. Sie eignen sich daher zur Mobilisierung pflanzeneigener Abwehrkräfte gegen Befall durch unerwünschte Mikroorganismen.The active compounds according to the invention also have a strong strengthening effect in plants. They are therefore suitable for mobilizing the plant's own defenses against attack by unwanted microorganisms.
Unter pflanzenstärkenden (resistenzinduzierenden) Stoffen sind im vorliegenden Zusammenhang solche Substanzen zu verstehen, die in der Lage sind, das Abwehrsystem von Pflanzen so zu stimulieren, dass die behandelten Pflanzen bei nachfolgender Inokulation mit unerwünschten Mikroorganismen weitgehende Resistenz gegen diese Mikroorganismen entfalten. Unter unerwünschten Mikroorganismen sind im vorliegenden Fall phytopathogene Pilze, Bakterien und Viren zu verstehen. Die erfindungsgemäßen Stoffe können also eingesetzt werden, um Pflanzen innerhalb eines gewissen Zeitraumes nach der Behandlung gegen den Befall durch die genannten Schaderreger zu schützen. Der Zeitraum, innerhalb dessen Schutz herbeigeführt wird, erstreckt sich im allgemeinen von 1 bis 10 Tage, vorzugsweise 1 bis 7 Tage nach der Behandlung der Pflanzen mit den Wirkstoffen.Plant-strengthening (resistance-inducing) substances are to be understood in the present context as substances which are able to stimulate the defense system of plants in such a way that the treated plants develop extensive resistance to these microorganisms when subsequently inoculated with undesired microorganisms. Undesired microorganisms are to be understood in the present case as phytopathogenic fungi, bacteria and viruses. The substances according to the invention can thus be used to protect plants against attack by the pests mentioned within a certain period of time after the treatment. The period of time within which protection is brought about generally extends from 1 to 10 days, preferably 1 to 7 days, after the plants have been treated with the active compounds.
Die gute Pflanzenverträglichkeit der Wirkstoffe in den zur Bekämpfung von Pflanzenkrankheiten notwendigen Konzentrationen erlaubt eine Behandlung von oberirdischen Pflanzenteilen, von Pflanz- und Saatgut, und des Bodens.The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases permits treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil.
Dabei lassen sich die erfindungsgemäßen Wirkstoffe mit besonders gutem Erfolg zur Bekämpfung von Getreidekrankheiten, wie beispielsweise gegen Puccinia-Arten und von Krankheiten im Wein-, Obst- und Gemüseanbau, wie beispielsweise gegen Botrytis-, Venturia- oder Alternaria-Arten, einsetzen.The active compounds according to the invention can be used with particularly good success for combating cereal diseases, for example against Puccinia species and for diseases in wine, fruit and vegetable cultivation, for example for botrytis, Venturia or Alternaria species.
Die erfindungsgemäßen Wirkstoffe eignen sich auch zur Steigerung des Ernteertrages. Sie sind außerdem mindertoxisch und weisen eine gute Pflanzenverträglichkeit auf.The active compounds according to the invention are also suitable for increasing the crop yield. They are also less toxic and have good plant tolerance.
Die erfindungsgemäßen Wirkstoffe können gegebenenfalls in bestimmten Konzentrationen und Aufwandmengen auch als Herbizide, zur Beeinflussung des Pflanzenwachstums, sowie zur Bekämpfung von tierischen Schädlingen verwendet werden. Sie lassen sich gegebenenfalls auch als Zwischen- und Vorprodukte für die Synthese weiterer Wirkstoffe einsetzen.If appropriate, the active compounds according to the invention can 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 compounds.
Erfindungsgemäß können alle Pflanzen und Pflanzenteile behandelt werden. Unter Pflanzen werden hierbei alle Pflanzen und Pflanzenpopulationen verstanden, wie erwünschte und unerwünschte Wildpflanzen oder Kulturpflanzen (einschließlich natürlich vorkommender Kulturpflanzen). Kulturpflanzen können Pflanzen sein, die durch konventionelle Züchtungs- und Optimierungsmethoden oder durch biotechnologische und gentechnologische Methoden oder Kombinationen dieser Methoden erhalten werden können, einschließlich der transgenen Pflanzen und einschließlich der durch Sorten- schutzrechte schützbaren oder nicht schützbaren Pflanzensorten. Unter Pflanzenteilen sollen alle oberirdischen und unterirdischen Teile und Organe der Pflanzen, wie Spross, Blatt, Blüte und Wurzel verstanden werden, wobei beispielhaft Blätter, Nadeln, Stängel, Stämme, Blüten, Fruchtkörper, Früchte und Samen sowie Wurzeln, Knollen und Rhizome aufgeführt werden. Zu den Pflanzenteilen gehört auch Erntegut sowie vegetatives und generatives Vermehrungsmaterial, beispielsweise Stecklinge, Knollen, Rhizome, Ableger und Samen. Die erfindungsgemäße Behandlung der Pflanzen und Pflanzenteile mit den Wirkstoffen erfolgt direkt oder durch Einwirkung auf deren Umgebung, Lebensraum oder Lagerraum nach den üblichenAccording to the invention, all plants and parts of plants can be treated. Plants are understood here to mean 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 cultivars which can or cannot be protected by plant breeders' rights. Plant parts are to be understood to mean all above-ground and underground parts and organs of plants, such as shoots, leaves, flowers and roots, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds. The treatment of the plants and parts of plants with the active compounds according to the invention is carried out directly or by acting on their surroundings, living space or storage space according to the customary methods
Behandlungsmethoden, z.B. durch Tauchen, Sprühen, Verdampfen, Vernebeln, Streuen, Aufstreichen und bei Vermehrungsmaterial, insbesondere bei Samen, weiterhin durch ein- oder mehrschichtiges Umhüllen.Treatment methods, e.g. by dipping, spraying, vaporizing, atomizing, scattering, spreading and, in the case of propagation material, in particular in the case of seeds, furthermore by coating in one or more layers.
Im Materialschutz lassen sich die erfindungsgemäßen Stoffe zum Schutz von technischen Materialien gegen Befall und Zerstörung durch unerwünschte Mikroorganismen einsetzen.In material protection, the substances according to the invention can be used to protect technical materials against attack and destruction by undesired microorganisms.
Unter technischen Materialien sind im vorliegenden Zusammenhang nichtlebende Materialien zu verstehen, die für die Verwendung in der Technik zubereitet worden sind. Beispielsweise können technische Materialien, die durch erfindungsgemäße Wirkstoffe vor mikrobieller Veränderung oder Zerstörung geschützt werden sollen, Klebstoffe, Leime, Papier und Karton, Textilien, Leder, Holz, Anstrichmittel und Kunststoffartikel, Kühlschmierstoffe und andere Materialien sein, die von Mikro- Organismen befallen oder zersetzt werden können. Im Rahmen der zu schützenden Materialien seien auch Teile von Produktionsanlagen, beispielsweise Kühlwasserkreisläufe, genannt, die durch Vermehrung von Mikroorganismen beeinträchtigt werden können. Im Rahmen der vorliegenden Erfindung seien als technische Materialien vorzugsweise Klebstoffe, Leime, Papiere und Kartone, Leder, Holz, Anstrichmittel, Kühlschmiermittel und Wärmeübertragungsflüssigkeiten genannt, besonders bevorzugt Holz.In the present context, technical materials are understood to mean non-living materials that have been prepared for use in technology. For example, technical materials which are to be protected against microbial change or destruction by active substances according to the invention can be adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which are attacked or decomposed by microorganisms can be. In the context of the materials to be protected, parts of production systems, for example cooling water circuits, are also mentioned which can be impaired by the multiplication of microorganisms. In the context of the present invention, technical materials are preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer liquids, particularly preferably wood.
Als Mikroorganismen, die einen Abbau oder eine Veränderung der technischen Materialien bewirken können, seien beispielsweise Bakterien, Pilze, Hefen, Algen und Schleimorganismen genannt. Vorzugsweise wirken die erfindungsgemäßen Wirkstoffe gegen Pilze, insbesondere Schimmelpilze, holzverfärbende und holzzerstörende Pilze (Basidiomyceten) sowie gegen Schleimorganismen und Algen.Bacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can cause degradation or a change in the technical materials. The active compounds according to the invention preferably act against fungi, in particular mold, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.
Es seien beispielsweise Mikroorganismen der folgenden Gattungen genannt:Microorganisms of the following genera may be mentioned, for example:
Alternaria, wie Alternaria tenuis, Aspergillus, wie Aspergillus niger,Alternaria, such as Alternaria tenuis, Aspergillus, such as Aspergillus niger,
Chaetomium, wie Chaetomium globosum,Chaetomium, like Chaetomium globosum,
Coniophora, wie Coniophora puetana,Coniophora, such as Coniophora puetana,
Lentinus, wie Lentinus tigrinus,Lentinus, such as Lentinus tigrinus,
Penicillium, wie Penicillium glaucum, Polyporus, wie Polyporus versicolor,Penicillium, such as Penicillium glaucum, Polyporus, such as Polyporus versicolor,
Aureobasidium, wie Aureobasidium pullulans, Sclerophoma, wie Sclerophoma pityophila,Aureobasidium, such as Aureobasidium pullulans, Sclerophoma, such as Sclerophoma pityophila,
Trichoderma, wie Trichoderma viride,Trichoderma, like Trichoderma viride,
Escherichia, wie Escherichia coli,Escherichia, such as Escherichia coli,
Pseudomonas, wie Pseudomonas aeruginosa, Staphylococcus, wie Staphylococcus aureus.Pseudomonas, such as Pseudomonas aeruginosa, Staphylococcus, such as Staphylococcus aureus.
Die Wirkstoffe können in Abhängigkeit von ihren jeweiligen physikalischen und/ oder chemischen Eigenschaften in die üblichen Formulierungen überführt werden, wie Lösungen, Emulsionen, Suspensionen, Pulver, Schäume, Pasten, Granulate, Aerosole, Feinstverkapselungen in polymeren Stoffen und in Hüllmassen für Saatgut, sowie ULV-Kalt- und Warmnebel-Formulierungen.Depending on their respective physical and / or chemical properties, the active ingredients can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV -Cold and warm mist formulations.
Diese Formulierungen werden in bekannter Weise hergestellt, z.B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln, unter Druck stehenden verflüssigten Gasen und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln. Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösungsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im Wesentlichen infrage: Aromaten, wie Xylol, Toluol oder Alkylnaphthaline, chlorierte Aromaten oder chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chlorethylene oder Methylenchlorid, aliphatische Kohlenwasser- stoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, Alkohole, wie Butanol oder Glycol sowie deren Ether und Ester, Ketone, wie Aceton, Methylethylketon, Methylisobutylketon oder Cyclohexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser. Mit verflüssigten gasformigen Streckmitteln oder Trägerstoffen sind solche Flüssigkeiten gemeint, welche bei normaler Temperatur und unter Normaldruck gasförmig sind, z.B. Aerosol- Treibgase, wie Halogenkohlenwasserstoffe sowie Butan, Propan, Stickstoff und Kohlendioxid. Als feste Trägerstoffe kommen infrage: z.B. natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate. Als feste Trägerstoffe für Granulate kommen infrage: z.B. gebrochene und fraktionierte natürliche Gesteine wie Calcit, Bims, Marmor, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehl, Kokosnussschalen, Maiskolben und Tabakstängel. Als Emulgier und/oder schaumerzeugende Mittel kommen infrage: z.B. nichtionogene und anionische Emulgatoren, wie Polyoxyethylen-Fettsäureester, Polyoxyethylen-Fettalkoholether, z.B. Alkylaryl- polyglycolether, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate. Als Disper- giermittel kommen infrage: z.B. Lignin-Sulfitablaugen und Methylcellulose. Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natürliche und synthetische pulverige, körnige oder latexformige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospholipide, wie Kephaline und Lecithine, und synthetische Phospholipide. Weitere Additive können mineralische und vegetabile Öle sein.These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water. Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide. Solid carrier materials come into question: for example natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates. Solid carriers for granules are possible: e.g. broken and fractionated natural rocks such as calcite, pumice, marble, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems. Possible emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates. Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose. Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.
Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo- und Metallphthalocyaninfarbstoffe und Spurermährstoffe, wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden.Dyes such as inorganic pigments, e.g. 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.
Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen 0,5 und 90 %.The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
Die erfindungsgemäßen Wirkstoffe können als solche oder in ihren Formulierungen auch in Mischung mit bekannten Fungiziden, Bakteriziden, Akariziden, Nematiziden oder Insektiziden verwendet werden, um so z.B. das Wirkungsspektrum zu verbreitern oder Resistenzentwicklungen vorzubeugen. In vielen Fällen erhält man dabei synergistische Effekte, d.h. die Wirksamkeit der Mischung ist größer als die Wirksamkeit der Einzelkomponenten.The active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to to broaden the spectrum of activity or to prevent the development of resistance. In many cases, synergistic effects are obtained, i.e. the effectiveness of the mixture is greater than the effectiveness of the individual components.
Als Mischpartner kommen zum Beispiel folgende Verbindungen infrage: Fungizide:The following compounds can be considered as mixing partners: Fungicides:
2-Phenylphenol; 8-Hydroxychinolinsulfat; Acibenzolar-S-methyl; Aldimorph; Amidoflumet; Am- propylfos; Ampropylfos-potassium; Andoprim; Anilazine; Azaconazole; Azoxystrobin; Benalaxyl; Benodanil; Benomyl; Benthiavalicarb-isopropyl; Benzamacril; Benzamacril-isobutyl; Bilanafos; Binapacryl; Biphenyl; Bitertanol; Blasticidin-S; Bromuconazole; Bupirimate; Buthiobate; Butylamin; Calcium polysulfide; Capsimycin; Captafol; Captan; Carbendazim; Carboxin; Carpropamid; Carvo- ne; Chinomethionat; Chlobenthiazone; Chlorfenazole; Chloroneb; Chlorothalonil; Chlozolinate; Clo- zylacon; Cyazofamid; Cyflufenamid; Cymoxanil; Cyproconazole; Cyprodinil; Cyprofuram; Dag- ger G; Debacarb; Dichlofluanid; Dichlone; Dichlorophen; Diclocymet; Diclomezine; Dicloran; Diethofencarb; Difenoconazole; Diflumetorim; Dimethirimol; Dimethomoφh; Dimoxystrobin; Dini- conazole; Diniconazole-M; Dinocap; Diphenylamine; Dipyrithione; Ditalimfos; Dithianon; Dodine; Drazoxolon; Edifenphos; Epoxiconazole; Ethaboxam; Ethirimol; Etridiazole; Famoxadone; Fenami- done; Fenapanil; Fenarimol; Fenbuconazole; Fenfuram; Fenhexamid; Fenitropan; Fenoxanil; Fenpi- clonil; Fenpropidin; Fenpropimoφh; Ferbam; Fluazinam; Flubenzimine; Fludioxonil; Flumetover; Flumoφh; Fluoromide; Fluoxastrobin; Fluquinconazole; Fluφrimidol; Flusilazole; Flusulfamide; Flutolanil; Flutriafol; Folpet; Fosetyl-Al; Fosetyl-sodium; Fuberidazole; Furalaxyl; Furametpyr; Furcarbanil; Furmecyclox; Guazatine; Hexachlorobenzene; Hexaconazole; Hymexazol; Imazalil; Imibenconazole; hninoctadine triacetate; hninoctadine tris(albesil; Iodocarb; Ipconazole; Iprobenfos;2-phenylphenol; 8-hydroxyquinoline sulfate; Acibenzolar-S-methyl; aldimorph; amidoflumet; Amopropylfos; Ampropylfos-potassium; andoprim; anilazine; azaconazole; azoxystrobin; benalaxyl; Benodanil; benomyl; Benthiavalicarb-isopropyl; Benzamacril; Benzamacril-isobutyl; bilanafos; binapacryl; biphenyl; bitertanol; Blasticidin-S; bromuconazole; Bupirimate; Buthiobate; butylamine; Calcium polysulfide; capsimycin; captafol; captan; carbendazim; carboxin; carpropamid; Carvone; chinomethionat; Chlobenthiazone; Chlorfenazole; chloroneb; chlorothalonil; chlozolinate; Clozylacon; cyazofamid; cyflufenamid; cymoxanil; cyproconazole; cyprodinil; cyprofuram; Dagger G; debacarb; dichlofluanid; dichlone; dichlorophen; diclocymet; Diclomezine; dicloran; diethofencarb; Difenoconazole; diflumetorim; dimethirimol; Dimethomoφh; dimoxystrobin; Diniconazole; Diniconazole-M; dinocap; diphenylamines; Dipyrithione; Ditalimfos; dithianon; dodine; Drazoxolon; edifenphos; epoxiconazole; ethaboxam; ethirimol; etridiazole; famoxadone; Fenami-done; Fenapanil; fenarimol; Fenbuconazole; fenfuram; fenhexamid; Fenitropan; fenoxanil; Fenpi-clonil; fenpropidin; Fenpropimoφh; ferbam; fluazinam; Flubenzimine; fludioxonil; flumetover; Flumoφh; fluoromides; fluoxastrobin; fluquinconazole; Fluφrimidol; flusilazole; flusulfamide; flutolanil; flutriafol; folpet; Fosetyl-Al; Fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; Furcarbanil; Furmecyclox; guazatine; Hexachlorobenzene; hexaconazole; hymexazol; imazalil; Imibenconazole; hninoctadine triacetate; hninoctadine tris (albesil; iodocarb; ipconazole; iprobefos;
Iprodione; Iprovalicarb; Irumamycin; Isoprothiolane; Isovaledione; Kasugamycin; Kresoxim-methyl;iprodione; iprovalicarb; Irumamycin; isoprothiolane; Isovaledione; kasugamycin; Kresoxim-methyl;
Mancozeb; Maneb; Meferimzone; Mepanipyrim; Mepronil; Metalaxyl; Metalaxyl-M; Metconazole;mancozeb; maneb; Meferimzone; mepanipyrim; mepronil; metalaxyl; Metalaxyl-M; metconazole;
Methasulfocarb; Methfuroxam; Metiram; Metominostrobin; Metsulfovax; Mildiomycin; Myclobuta- nil; Myclozolin; Natamycin; Nicobifen; Nitrothal-isopropyl; Noviflumuron; Nuarimol; Ofurace;methasulfocarb; Methfuroxam; metiram; metominostrobin; Metsulfovax; mildiomycin; Myclobutanil; myclozoline; natamycin; nicobifen; Nitro Thal-isopropyl; Noviflumuron; nuarimol; ofurace;
Orysastrobin; Oxadixyl; Oxolinic acid; Oxpoconazole; Oxycarboxin; Oxyfenthiin; Paclobutrazol;orysastrobin; oxadixyl; Oxolinic acid; Oxpoconazole; oxycarboxin; Oxyfenthiin; paclobutrazol;
Pefurazoate; Penconazole; Pencycuron; Phosdiphen; Phthalide; Picoxystrobin; Piperalin; Polyoxins;Pefurazoate; penconazole; pencycuron; phosdiphen; phthalides; picoxystrobin; piperalin; Polyoxins;
Polyoxorim; Probenazole; Prochloraz; Procymidone; Propamocarb; Propanosine-sodium; Propicon- azole; Propineb; Proquinazid; Prothioconazole; Pyraclostrobin; Pyrazophos; Pyrifenox; Pyrimethanil; Pyroquilon; Pyroxyfur; Pyrrolnitrine; Quinconazole; Quinoxyfen; Quintozene; Simeconazole; Spi- roxamine; Sulfbr; Tebuconazole; Tecloftalam; Tecnazene; Tetcyclacis; Tetraconazole; Thiabenda- zole; Thicyofen; Thifluzamide; Thiophanate-methyl; Thiram; Tioxymid; Tolclofos-methyl; Tolylflu- anid; Triadimefon; Triadimenol; Triazbutil; Triazoxide; Tricyclamide; Tricyclazole; Tridemoφh; Trifloxystrobin; Triflumizole; Triforine; Triticonazole; Uniconazole; Validamycin A; Vinclozolin; Zineb; Ziram; Zoxamide; (2S)-N-[2-[4-[[3-(4-Chlθφhenyl)-2-propinyl]oxy]-3-methoxyphenyl]- ethyl]-3-methyl-2-[(methylsulfonyl)amino]-butanamid; l-(l-Naphthalenyl)-lH-pyrrol-2,5-dion;Polyoxorim; Probenazole; prochloraz; procymidone; propamocarb; Propanosine-sodium; Propiconazoles; propineb; proquinazid; prothioconazole; pyraclostrobin; Pyrazohos; pyrifenox; pyrimethanil; pyroquilon; Pyroxyfur; Pyrrolnitrine; Quinconazole; quinoxyfen; quintozene; Simeconazole; Spiroxamine; Sulfbr; tebuconazole; tecloftalam; Tecnazene; Tetcyclacis; tetraconazole; Thiabendazole; Thicyofen; Thifluzamide; Thiophanate-methyl; thiram; Tioxymid; Tolclofos-methyl; Tolylfluoride; triadimefon; triadimenol; Triazbutil; triazoxide; Tricyclamide; Tricyclazole; Tridemoφh; trifloxystrobin; triflumizole; triforine; triticonazole; Uniconazole; Validamycin A; vinclozolin; Zineb; ziram; zoxamide; (2S) -N- [2- [4 - [[3- (4-Chlθφhenyl) -2-propynyl] oxy] -3-methoxyphenyl] - ethyl] -3-methyl-2 - [(methylsulfonyl) amino] - butanamide; l- (l-naphthalenyl) -lH-pyrrole-2,5-dione;
2,3,5,6-Tetrachlor-4-(methylsulfonyl)-pyridin; 2-Amino-4-methyl-N-phenyl-5-thiazolcarboxamid; 2- Chlor-N-(2,3-dihydro-l,l,3-trimethyl-lH-inden-4-yl)-3-pyridincarboxamide; 3,4,5-Trichlor-2,6-pyri- dindicarbonitril; Actinovate; cis-l-(4-Chloφhenyl)-2-(lH-l,2,4-triazol-l-yl)-cycloheptanol; Methyl l-(2,3-dihydro-2,2-dimethyl-lH-inden-l-yl)-lH-imidazol-5-carboxylat; Monokaliumcarbonat; N-(6- Methoxy-3-pyridinyl)-cyclopropancarboxamid; N-Butyl-8-(l,l-dimethylethyl)-l-oxaspiro[4.5]de- can-3-amin; Natriumtetrathiocarbonat; sowie Kupfersalze und -Zubereitungen, wie Bordeaux mix- ture; Kupferhydroxid; Kupfernaphthenat; Kupferoxychlorid; Kupfersulfat; Cufraneb; Kupferoxid; Mancopper; Oxine-copper.2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyridine; 2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide; 2-chloro-N- (2,3-dihydro-l, l, 3-trimethyl-lH-inden-4-yl) -3-pyridinecarboxamide; 3,4,5-trichloro-2,6-pyridinedicarbonitrile; Actinovate; cis-l- (4-Chloφhenyl) -2- (lH-l, 2,4-triazol-l-yl) cycloheptanol; Methyl l- (2,3-dihydro-2,2-dimethyl-1H-inden-1-yl) -IH-imidazole-5-carboxylate; Monokaliumcarbonat; N- (6-methoxy-3-pyridinyl) cyclopropanecarboxamide; N-butyl-8- (l, l-dimethylethyl) -l-oxaspiro [4.5] decan-3-amine; sodium tetrathiocarbonate; as well as copper salts and preparations, such as Bordeaux mixture; copper; copper naphthenate; copper oxychloride; Copper sulfate; Cufraneb; copper; mancopper; Oxine-copper.
Bakterizide:bactericides:
Bronopol, Dichlorophen, Nitrapyrin, Nickel-dimethyldithiocarbamat, Kasugamycin, Octhilinon, Furancarbonsäure, Oxytetracyclin, Probenazol, Streptomycin, Tecloftalam, Kupfersulfat und andere Kupfer-Zubereitungen.Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.
Insektizide / Akarizide / Nematizide:Insecticides / acaricides / nematicides:
Abamectin, ABG-9008, Acephate, Acequinocyl, Acetamiprid, Acetoprole, Acrinathrin, AKD-1022, AKD-3059, AKD-3088, Alanycarb, Aldicarb, Aldoxycarb, Allethrin, Allethrin lR-isomers, Alpha- Cypermethrin (Alphamethrin), Amidoflumet, Aminocarb, Amitraz, Avermectin, AZ-60541, Aza- dirachtin, Azamethiphos, Azinphos-methyl, Azinphos-ethyl, Azocyclotin, Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Bacillus thuringiensis strain EG-2348, Bacillus thuringiensis strain" GC-91, Bacillus thuringiensis strain NCTC-11821, Baculoviren, Beauveria bassiana, Beauveria tenella, Bendiocarb, Benfuracarb, Bensultap, Benzoximate, Beta-Cyfluthrin,Abamectin, ABG-9008, Acephate, Acequinocyl, Acetamiprid, Acetoprole, Acrinathrin, AKD-1022, AKD-3059, AKD-3088, Alanycarb, Aldicarb, Aldoxycarb, Allethrin, Allethrin lR-isomers, Alpha-Cidermlhrhrine Aminocarb, Amitraz, Avermectin, AZ-60541, Aza-dirachtin, Azamethiphos, Azinphos-methyl, Azinphos-ethyl, Azocyclotin, Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Bacillus thuringiensis strain EG-2348, EG-2348 thuringiensis strain " GC-91, Bacillus thuringiensis strain NCTC-11821, baculoviruses, Beauveria bassiana, Beauveria tenella, Bendiocarb, Benfuracarb, Bensultap, Benzoximate, Beta-Cyfluthrin,
Beta-Cypermethrin, Bifenazate, Bifenthrin, Binapacryl, Bioallethrin, Bioallethrin-S-cyclopentyl- isomer, Bioethanomethrin, Biopermethrin, Bioresmethrin, Bistrifluron, BPMC, Brofenprox, Bromo- phos-ethyl, Bromopropylate, Bromfenvinfos (-methyl), BTG-504, BTG-505, Bufencarb, Buprofezin,Beta-cypermethrin, bifenazate, bifenthrin, binapacryl, bioallethrin, bioallethrin-S-cyclopentyl-isomer, bioethanomethrin, biopermethrin, bioresmethrin, bistrifluron, BPMC, brofenprox, bromophosph-ethyl, bromopropyl-methyl-bromopropylate (50), bromopropylate, bromopropylate BTG-505, Bufencarb, Buprofezin,
Butathiofos, Butocarboxim, Butoxycarboxim, Butylpyridaben, Cadusafos, Camphechlor, Carbaryl,Butathiofos, Butocarboxim, Butoxycarboxim, Butylpyridaben, Cadusafos, Camphechlor, Carbaryl,
Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA-50439, Chinomethionat, Chlordane, Chlor- dimeform, Chloethocarb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlorme- phos, Chlorobenzilate, Chloropicrin, Chloφroxyfen, Chloφyrifos-methyl, Chloφyrifos (-ethyl), Chlovaporthrin, Chromafenozide, Cis-Cypermethrin, Cis-Resmethrin, Cis-Permethrin, Clocythrin, Cloethocarb, Clofentezine, Clothianidin, Clothiazoben, Codlemone, Coumaphos, Cyanofenphos, Cyanophos, Cycloprene, Cycloprothrin, Cydia pomonella, Cyfluthrin, Cyhalothrin, Cyhexatin, Cy- permethrin, Cyphenothrin (lR-trans-isomer), Cyromazine, DDT, Deltamethrin, Demeton-S-methyl, Demeton-S-methylsulphon, Diafenthiuron, Dialifos, Diazinon, Dichlofenthion, Dichlorvos, Dicofol, Dicrotophos, Dicyclanil, Diflubenzuron, Dimethoate, Dimethylvinphos, Dinobuton, Dinocap, Dino- tefuran, Diofenolan, Disulfoton, Docusat-sodium, Dofenapyn, DOWCO-439, Eflusilanate, Ema- mectin, Emamectin-benzoate, Empenthrin (lR-isomer), Endosulfan, Entomopthora spp., EPN, Esfen- valerate, Ethiofencarb, Ethiprole, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimfos, Famphur, Fenamiphos, Fenazaquin, Fenbutatin oxide, Fenfluthrin, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fensulfothion, Fenthion, Fentrifanil, Fenvalerate, Fipronil, Flonicamid, Fluacrypyrim, Fluazuron, Flubenzimine, Flubrocythrinate, Flucycloxuron, Flucythrinate, Flufenerim, Flufenoxuron, Flufenprox, Flumethrin, Flupyrazofos, Flutenzin (Flufenzine), Fluvalinate, Fonofos, Formetanate, Formothion, Fosmethilan, Fosthiazate, Fubfenprox (Fluproxyfen), Furathiocarb, Gamma-HCH, Gossyplure, Grandlure, Granuloseviren, Halfenprox, Halofenozide, HCH, HCN-801, Heptenophos, Hexaflumuron, Hexy- thiazox, Hydramethylnone, Hydroprene, IKA-2002, Imidacloprid, Imiprothrin, Indoxacarb, Iodofen- phos, Iprobenfos, Isazofos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin, Japonilure, Kadethrin, Kernpolyederviren, Kinoprene, Lambda-Cyhalothrin, Lindane, Lufenuron, Malathion, Mecarbam, Mesulfenfos, Metaldehyd, Metam-sodium, Methacrifos, Methamidophos, Metharhizium anisopliae, Metharhizium flavoviride, Mefhidathion, Methiocarb, Methomyl, Methoprene, Methoxychlor, Methoxyfenozide, Metolcarb, Metoxadiazone, Mevinphos, Milbemectin, Milbemycin, MKI-245, MON-45700, Monocrotophos, Moxidectin, MTI-800, Naled, NC-104, NC-170, NC-184, NC-194, NC-196, Niclosamide, Nicotine, Nitenpyram, Nithiazine, NNI-0001, NNI-0101, NNI-0250, NNI- 9768, Novaluron, Noviflumuron, OK-5101, OK-5201, OK-9601, OK-9602, OK-9701, OK-9802, Omethoate, Oxamyl, Oxydemeton-methyl, Paecilomyces fumosoroseus, Parathion-methyl, Parathion (-ethyl), Permethrin (eis-, trans-), Petroleum, PH-6045, Phenothrin (lR-trans isomer), Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidon, Phosphocarb, Phoxim, Piperonyl butoxide, Pirimicarb,Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA-50439, Chinomethionate, Chlordane, Chlorodimeform, Chloethocarb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlorme- phos, Chlorobenzilate, Chloropicrin, Chloφroxyosif, Chloφyrethylf, Chloφyrethylf, Chloφyrethylf, Chloφyrethylf, Chloφyrethylf, Chloφyrethylf, Chloφyrethylf) Chlovaporthrin, Chromafenozide, Cis-Cypermethrin, Cis-Resmethrin, Cis-Permethrin, Clocythrin, Cloethocarb, Clofentezine, Clothianidin, Clothiazoben, Codlemone, Coumaphos, Cyanofenphos, Cyanophos, Cycloprene, Cycloprothrinin, Cyhalhrothrin, Cyydhrinhrin, Cyydhrinhrin, Cydhalinhrin, Cydhalinhrin, Cydro , Cyphenothrin (lR-trans-isomer), Cyromazine, DDT, Deltamethrin, Demeton-S-methyl, Demeton-S-methylsulphone, Diafenthiuron, Dialifos, Diazinon, Dichlofenthion, Dichlorvos, Dicofol, Dicrotophos, Dicyclanilon, Dimethylvenzyluron, Dimethylvenzyluron Dinobuton, Dinocap, Dinotefuran, Diofenolan, Disulfoton, Docusat-sodium, Dofenapyn, DOWCO-439, Eflusilanate, Emamectin, Emamectin-Benzoate, Empenthrin (IR-isomer), Endosu lfan, Entomopthora spp., EPN, Esfenvalerate, Ethiofencarb, Ethiprole, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimfos, Famphur, Fenamiphos, Fenazaquin, Fenbutatin oxide, Fenfluthrin, Fenitrothion, Fenocucarboxy, FenoxiPhroxin, FenoxiPhrin, FenoxiPhrin, FenoxiPhrin, FenoxiPhroxin, FenoxiPhrin, Fenoxi, Prox , Fenpyrithrin, fenpyroximate, fensulfothion, fenthion, Fentrifanil, fenvalerate, fipronil, flonicamid, fluacrypyrim, fluazuron, Flubenzimine, Flubrocythrinate, flucycloxuron, Flucythrinate, flufenerim, flufenoxuron, flufenprox, flumethrin, Flupyrazofos, Flutenzin (Flufenzine), fluvalinate, fonofos, Formetanate, Formothion, Fosmethilan, Fosthiazate, Fubfenprox (Fluproxyfen), Furathiocarb, Gamma-HCH, Gossyplure, Grandlure, Granuloseviren, Halfenprox, Halofenozide, HCH, HCN-801, Heptenophos, Hexaflumuron, Hexyethylthiazone, Hydramene, Hydramenoxid, 2002. , Imiprothrin, Indoxacarb, Iodofenphos, Iprobefos, Isazofos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin, Japonilure, Kadethrin, Kernpolyederv iren, kinoprene, lambda-cyhalothrin, lindane, lufenuron, malathion, mecarbam, mesulfenfos, metaldehyde, metam-sodium, methacrifos, methamidophos, metharhician anisopliae, metharhician flavoviride, mefhidathione, methiocarb, methomoxy, methoxoloxy, methoprene zone, Mevinphos, Milbemectin, Milbemycin, MKI-245, MON-45700, Monocrotophos, Moxidectin, MTI-800, Naled, NC-104, NC-170, NC-184, NC-194, NC-196, Niclosamide, Nicotine, Nitenpyram, Nithiazine, NNI-0001, NNI-0101, NNI-0250, NNI- 9768, Novaluron, Noviflumuron, OK-5101, OK-5201, OK-9601, OK-9602, OK-9701, OK-9802, Omethoate, Oxamyl, Oxydemeton-methyl, Paecilomyces fumosoroseus, Parathion-methyl, Parathion (-ethyl), Permethrin (eis, trans-), Petroleum, PH-6045, Phenothrin (lR-trans isomer), Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidon, Phosphocarb, Phoxim, Piperonyl butoxide, Pirimicarb,
Pirimiphos-methyl, Pirimiphos-ethyl, Prallethrin, Profenofos, Promecarb, Propaphos, Propargite,Pirimiphos-methyl, Pirimiphos-ethyl, Prallethrin, Profenofos, Promecarb, Propaphos, Propargite,
Propetamphos, Propoxur, Prothiofos, Prothoate, Protrifenbute, Pymetrozine, Pyraclofos, Pyres- methrin, Pyrethrum, Pyridaben, Pyridalyl, Pyridaphenthion, Pyridathion, Pyrimidifen, Pyriproxyfen, Quinalphos, Resmethrin, RH-5849, Ribavirin, RU-12457, RU-15525, S-421, S-1833, Salithion,Propetamphos, Propoxur, Prothiofos, Prothoate, Protrifenbute, Pymetrozine, Pyraclofos, Pyresmethrin, Pyrethrum, Pyridaben, Pyridalyl, Pyridaphenthion, Pyridathion, Pyrimidifen, Pyriproxyfen, Quinalphos, Resmethrin, RH -725, RU-575, RU-575, RU-575, RU-575, RU-575, RU-R525, RU-575, RU-575, RU-R525, RU-255, RU-575, RU-R525, RU-255 S-421, S-1833, Salithion,
Sebufos, SI-0009, Silafluofen, Spinosad, Spirodiclofen, Spiromesifen, Sulfluramid, Sulfotep, Sulpro- fos, SZI-121, Tau-Fluvalinate, Tebufenozide, Tebufenpyrad, Tebupirimfos, Teflubenzuron, Teflu- thrin, Temephos, Temivinphos, Terbam, Terbufos, Tetrachlorvinphos, Tetradifon, Tetramethrin,Sebufos, SI-0009, Silafluofen, Spinosad, Spirodiclofen, Spiromesifen, Sulfluramid, Sulfotep, Sulprofos, SZI-121, Tau-Fluvalinate, Tebufenozide, Tebufenpyrad, Tebupirimfos, Teflubenzuron, Teflu- threrbam, Tefufos, Temphos, Temephos, Temephos, Temephos Tetrachlorvinphos, tetradifon, tetramethrin,
Tetramethrin (lR-isomer), Tetrasul, Theta-Cypermethrin, Thiacloprid, Thiamethoxam, Thiapronil, Thiatriphos, Thiocyclam hydrogen oxalate, Thiodicarb, Thiofanox, Thiometon, Thiosultap-sodium, Thuringiensin, Tolfenpyrad, Tralocythrin, Tralomethrin, Transfluthrin, Triarathene, Triazamate, Tri- azophos, Triazuron, Trichlophenidine, Trichlorfon, Triflumuron, Trimethacarb, Vamidothion, Vaniliprole, Verbutin, Verticillium lecanii, WL-108477, WL-40027, YI-5201, YI-5301, YI-5302, XMC, Xylylcarb, ZA-3274, Zeta-Cypermethrin, Zolaprofos, ZXI-8901, die Verbindung 3-Methyl- phenyl-propylcarbamat (Tsumacide Z), die Verbindung 3-(5-Chlor-3-pyridinyl)-8-(2,2,2-trifluor- ethyl)-8-azabicyclo[3.2.1]octan-3-carbonitril (CAS-Reg.-Nr. 185982-80-3) imd das entsprechende 3- endo-Isomere (CAS-Reg.-Nr. 185984-60-5) (vgl. WO-96/37494, WO-98/25923), sowie Präparate, welche insektizid wirksame Pflanzenextrakte, Nematoden, Pilze oder Viren enthalten.Tetramethrin (lR-isomer), Tetrasul, Theta-Cypermethrin, Thiacloprid, Thiamethoxam, Thiapronil, Thiatriphos, Thiocyclam hydrogen oxalate, Thiodicarb, Thiofanox, Thiometon, Thiosultap-sodium, Thuringiensin, Trolomomethhrinin, Trolfenomhrhrinin, Trolfenpyradin, Trolfenpyradin, Trolfenpyradine, - azophos, triazuron, trichlophenidine, trichlorfon, triflumuron, trimethacarb, vamidothion, vaniliprole, verbutin, verticillium lecanii, WL-108477, WL-40027, YI-5201, YI-5301, YI-5302, Xcarb, XMC, XMC, XMC, XMC, XMC Zeta-cypermethrin, Zolaprofos, ZXI-8901, the compound 3-methylphenyl-propylcarbamate (Tsumacide Z), the compound 3- (5-chloro-3-pyridinyl) -8- (2,2,2-trifluoro-ethyl ) -8-azabicyclo [3.2.1] octane-3-carbonitrile (CAS Reg. No. 185982-80-3) and the corresponding 3-endo isomer (CAS Reg. No. 185984-60-5 ) (cf. WO-96/37494, WO-98/25923), and preparations which contain insecticidally active plant extracts, nematodes, fungi or viruses.
Auch eine Mischung mit anderen bekannten Wirkstoffen, wie Herbiziden oder mit Düngemitteln und Wachstumsregulatoren, Safener bzw. Semiochemicals ist möglich.A mixture with other known active compounds, such as herbicides or with fertilizers and growth regulators, safeners or semiochemicals, is also possible.
Darüber hinaus weisen die erfindungsgemäßen Verbindungen der Formel (I) auch sehr gute antimykotische Wirkungen auf. Sie besitzen ein sehr breites antimykotisches Wirkungsspektrum, insbesondere gegen Dermatophyten und Sprosspilze, Schimmel imd diphasische Pilze (z.B. gegen Candida-Spezies wie Candida albicans, Candida glabrata) sowie Epidermophyton floccosum, Aspergillus-Spezies wie Aspergillus niger und Aspergillus fumigatus, Trichophyton-Spezies wie Trichophyton mentagrophytes, Microsporon-Spezies wie Microsporon canis und audouinii. Die Aufzählung dieser Pilze stellt keinesfalls eine Beschränkung des erfassbaren mykotischen Spektrums dar, sondern hat nur erläuternden Charakter.In addition, the compounds of the formula (I) according to the invention also have very good antifungal effects. They have a very broad spectrum of antifungal effects, in particular against dermatophytes and shoot fungi, mold and diphasic fungi (e.g. against Candida species such as Candida albicans, Candida glabrata) as well as Epidermophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillichophophytony fumigton, fumigatus and Fumigyus mentagrophytes, microsporon species such as microsporon canis and audouinii. The list of these fungi in no way represents a limitation of the detectable mycotic spectrum, but is only of an explanatory nature.
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder den daraus bereiteten Anwendungsformen, wie gebrauchsfertige Lösungen, Suspensionen, Spritzpulver, Pasten, lösliche Pulver, Stäubemittel und Granulate angewendet werden. Die Anwendung geschieht in üblicher Weise, z.B. durch Gießen, Verspritzen, Versprühen, Verstreuen, Verstäuben, Verschäumen, Bestreichen usw. Es ist ferner möglich, die Wirkstoffe nach dem Ultra-Low- Volume-Verfahren aus- zubringen oder die Wirkstoffzubereitung oder den Wirkstoff selbst in den Boden zu injizieren. Es kann auch das Saatgut der Pflanzen behandelt werden.The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the customary manner, for example by watering, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to remove the active ingredients using the ultra-low-volume process. bring or inject the drug preparation or the drug itself into the soil. The seeds of the plants can also be treated.
Beim Einsatz der erfindungsgemäßen Wirkstoffe als Fungizide können die Aufwandmengen je nach Applikationsart innerhalb eines größeren Bereiches variiert werden. Bei der Behandlung von Pflanzenteilen liegen die Aufwandmengen an Wirkstoff im allgemeinen zwischen 0,1 und 10.000 g/ha, vorzugsweise zwischen 10 und 1.000 g/ha. Bei der Saatgutbehandlung liegen die Aufwandmengen an Wirkstoff im allgemeinen zwischen 0,001 und 50 g pro Kilogramm Saatgut, vorzugsweise zwischen 0,01 und 10 g pro Kilogramm Saatgut. Bei der Behandlung des Bodens liegen die Aufwandmengen an Wirkstoff im allgemeinen zwischen 0,1 und 10.000 g/ha, vorzugsweise zwischen 1 und 5.000 g/ha.When the active compounds according to the invention are used as fungicides, the application rates can be varied within a relatively wide range, depending on the type of application. In the treatment of parts of plants, the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha. In the case of seed treatment, the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. In the treatment of the soil, the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.
Wie bereits oben erwähnt, können erfϊndungsgemäß alle Pflanzen und deren Teile behandelt werden. In einer bevorzugten Ausführungsform werden wild vorkommende oder durch konventionelle biologische Zuchtmethoden, wie Kreuzung oder Protoplastenfusion erhaltenen Pflanzenarten und Pflanzensorten sowie deren Teile behandelt. In einer weiteren bevorzugten Ausführungsform werden transgene Pflanzen und Pflanzensorten, die durch gentechnologische Methoden gegebenenfalls in Kombination mit konventionellen Methoden erhalten wurden (Genetically Modified Organisms) und deren Teile behandelt. Der Begriff „Teile" bzw. „Teile von Pflanzen" oder „Pflanzenteile" wurde oben erläutert.As already mentioned above, according to the invention, all plants and their parts can be treated. In a preferred embodiment, wild plant species or plant species and their parts obtained by conventional biological breeding methods, such as crossing or protoplast fusion, are treated. In a further preferred embodiment, transgenic plants and plant cultivars which have been obtained by genetic engineering methods, if appropriate in combination with conventional methods (genetically modified organisms) and their parts are treated. The term “parts” or “parts of plants” or “parts of plants” was explained above.
Besonders bevorzugt werden erfindungsgemäß Pflanzen der jeweils handelsüblichen oder in Gebrauch befindlichen Pflanzensorten behandelt. Unter Pflanzensorten versteht man Pflanzen mit neuen Eigenschaften („Traits"), die sowohl durch konventionelle Züchtung, durch Mutagenese oder durch rekombinante DNA-Techniken gezüchtet worden sind. Dies können Sorten, Rassen, Bio- und Genotypen sein.Plants of the plant varieties which are in each case commercially available or in use are particularly preferably treated according to the invention. Plant cultivars are understood to mean plants with new properties (“traits”) which have been cultivated by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be cultivars, breeds, bio- and genotypes.
Je nach Pflanzenarten bzw. Pflanzensorten, deren Standort und Wachstumsbedingungen (Böden, Klima, Vegetationsperiode, Ernährung) können durch die erfindungsgemäße Behandlung auch überadditive („synergistische") Effekte auftreten. So sind beispielsweise erniedrigte Aufwandmengen und oder Erweiterungen des Wirkungsspektrums und/oder eine Verstärkung der Wirkung der erfindungsgemäß verwendbaren Stoffe und Mittel, besseres Pflanzenwachstum, erhöhte Toleranz gegenüber hohen oder niedrigen Temperaturen, erhöhte Toleranz gegen Trockenheit oder gegen Wasser- bzw. Bodensalzgehalt, erhöhte Blühleistung, erleichterte Ernte, Beschleunigung der Reife, höhere Ernteerträge, höhere Qualität und/oder höherer Ernährungswert der Ernteprodukte, höhere Lagerfahigkeit und/oder Bearbeitbarkeit der Ernteprodukte möglich, die über die eigentlich zu erwartenden Effekte hinausgehen.Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, growing season, nutrition), the treatment according to the invention can also result in superadditive (“synergistic”) effects. For example, reduced application rates and or widening the spectrum of action and / or strengthening the effect of the substances and agents which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to dryness or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripeness, higher harvest yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or workability of the harvested products possible, which is actually about the expected effects go beyond.
Zu den bevorzugten erfindungsgemäß zu behandelnden transgenen (gentechnologisch erhaltenen) Pflanzen bzw. Pflanzensorten gehören alle Pflanzen, die durch die gentechnologische Modifikation genetisches Material erhielten, welches diesen Pflanzen besondere vorteilhafte wertvolle Eigenschaften („Traits") verleiht. Beispiele für solche Eigenschaften sind besseres Pflanzenwachstum, erhöhte Toleranz gegenüber hohen oder niedrigen Temperaturen, erhöhte Toleranz gegen Trockenheit oder gegen Wasser- bzw. Bodensalzgehalt, erhöhte Blühleistung, erleichterte Ernte, Beschleunigimg der Reife, höhere Ernteerträge, höhere Qualität und/oder höherer Ernährungswert der Erntepro- dukte, höhere Lagerfahigkeit und/oder Bearbeitbarkeit der Ernteprodukte. Weitere und besonders hervorgehobene Beispiele für solche Eigenschaften sind eine erhöhte Abwehr der Pflanzen gegen tierische und mikrobielle Schädlinge, wie gegenüber Insekten, Milben, pflanzenpathogenen Pilzen, Bakterien und/oder Viren sowie eine erhöhte Toleranz der Pflanzen gegen bestimmte herbizide Wirkstoffe. Als Beispiele transgener Pflanzen werden die wichtigen Kultuφflanzen, wie Getreide (Weizen, Reis), Mais, Soja, Kartoffel, Baumwolle, Tabak, Raps sowie Obstpflanzen (mit den Früchten Äpfel, Birnen, Zitrusfrüchten und Weintrauben) erwähnt, wobei Mais, Soja, Kartoffel, Baumwolle, Tabak und Raps besonders hervorgehoben werden. Als Eigenschaften („Traits") werden besonders hervorgehoben die erhöhte Abwehr der Pflanzen gegen Insekten, Spinnentiere, Namatoden und Schnecken durch in den Pflanzen entstehende Toxine, insbesondere solche, die durch das genetische Material aus Bacillus Thuringiensis (z.B. durch die Gene CryΙA(a), CryIA(b), CryΙA(c), CryllA, CrylHA, CryIHB2, Cry9c Cry2Ab, Cry3Bb und CrylF sowie deren Kombinationen) in den Pflanzen erzeugt werden (im folgenden "Bt Pflanzen"). Als Eigenschaften („Traits") werden auch besonders hervorgehoben die erhöhte Abwehr von Pflanzen gegen Pilze, Bakterien und Viren durch Systemische Akquirierte Resistenz (SAR), Systemin, Phytoalexine, Elicitoren sowie Resistenzgene und entsprechend exprimierte Proteine und Toxine. Als Eigenschaften („Traits") werden weiterhin besonders hervorgehoben die erhöhte Toleranz der Pflanzen gegenüber bestimmten herbiziden Wirkstoffen, z.B. Imidazolinonen, Sulfonylharnstoffen, Glyphosate oder Phosphinotricin (z.B. "PAT"- Gen). Die jeweils die gewünschten Eigenschaften („Traits") verleihenden Gene können auch in Kombinationen miteinander in den transgenen Pflanzen vorkommen. Als Beispiele für "Bt Pflanzen" seien Maissorten, Baumwollsorten, Sojasorten und Kartoffelsorten genannt, die unter den Handelsbezeichnungen YIELD GARD® (z.B. Mais, Baumwolle, Soja), KnockOut® (z.B. Mais), StarLink® (z.B. Mais), Bollgard® (Baumwolle), Nucoton® (Baumwolle) und NewLeaf® (Kartoffel) vertrieben werden. Als Beispiele für Herbizid tolerante Pflanzen seien Maissorten, Baumwollsorten und Sojasorten genannt, die unter den Handelsbezeichnungen Roundup Ready® (Toleranz gegen Glyphosate z.B. Mais, Baumwolle, Soja), Liberty Link® (Toleranz gegen Phosphinotricin, z.B. Raps), IMI® (Toleranz gegen Imidazolinone) und STS® (Toleranz gegen Sulfonylharnstoffe z.B. Mais) vertrieben werden. Als Herbizid resistente (konventionell auf Herbizid-Toleranz gezüchtete) Pflanzen seien auch die unter der Bezeichnung Clearfield® vertriebenen Sorten (z.B. Mais) erwähnt. Selbstverständlich gelten diese Aussagen auch für in der Zukunft entwickelte bzw. zukünftig auf den Markt kommende Pflanzensorten mit diesen oder zukünftig entwickelten genetischen Eigenschaften („Traits").The preferred transgenic plants or plant cultivars to be treated according to the invention include all plants which have received genetic material through the genetic engineering modification, which gives these plants particularly advantageous valuable properties (“traits”). Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripeness, higher harvest yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or Machinability of the harvested products Further and particularly highlighted examples of such properties are an increased defense of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and / or vire n and an increased tolerance of the plants to certain herbicidal active ingredients. Examples of transgenic plants are the important cultivated plants, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, tobacco, rapeseed and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with corn, soybeans, potatoes , Cotton, tobacco and rapeseed are highlighted. The traits are particularly emphasized as the increased defense of the plants against insects, arachnids, namatodes and snails by toxins which arise in the plants, in particular those which are caused by the genetic material from Bacillus thuringiensis (eg by the genes CryΙA (a) , CryIA (b), CryΙA (c), CryllA, CrylHA, CryIHB2, Cry9c Cry2Ab, Cry3Bb and CrylF as well as their combinations) are produced in the plants (hereinafter referred to as "Bt plants"). Properties ("traits") are also used the increased defense of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors as well as resistance genes and correspondingly expressed proteins and toxins are particularly emphasized. The properties (“traits”) which are particularly emphasized are the increased tolerance of the plants to certain herbicidal active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (for example “PAT” gene). The genes conferring the desired properties (“traits”) can also occur in combinations with one another in the transgenic plants. Examples of "Bt plants" are maize varieties, cotton varieties, soy varieties and potato varieties that are marketed under the trade names YIELD GARD® (e.g. corn, cotton, soy), KnockOut® (e.g. corn), StarLink® (e.g. corn), Bollgard® ( Cotton), Nucoton® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants are maize varieties, cotton varieties and soy varieties that are marketed under the trade names Roundup Ready® (tolerance to glyphosate e.g. corn, cotton, soy), Liberty Link® (tolerance to phosphinotricin, e.g. rapeseed), IMI® (tolerance to Imidazolinone) and STS® (tolerance to sulfonylureas such as maize) become. The herbicide-resistant plants (conventionally bred to herbicide tolerance) include the varieties sold under the name Clearfield® (eg maize). Of course, these statements also apply to plant varieties developed in the future or coming onto the market in the future with these or future-developed genetic properties ("traits").
Die aufgeführten Pflanzen können besonders vorteilhaft erfindungsgemäß mit den Verbindimgen der allgemeinen Formel (I) bzw. den erfindungsgemäßen Wirkstoffmischungen behandelt werden. Die bei den Wirkstoffen bzw. Mischungen oben angegebenen Vorzugsbereiche gelten auch für die Behandlung dieser Pflanzen. Besonders hervorgehoben sei die Pflanzenbehandlung mit den im vorliegenden Text speziell aufgeführten Verbindungen bzw. Mischungen.The plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula (I) or the active compound mixtures according to the invention. The preferred ranges given above for the active substances or mixtures also apply to the treatment of these plants. Plant treatment with the compounds or mixtures specifically listed in the present text should be particularly emphasized.
Die Herstellung und die Verwendung der erfindungsgemäßen Wirkstoffe geht aus den folgenden Beispielen hervor. The preparation and use of the active compounds according to the invention can be seen from the following examples.
HerstellungsbeispielePreparation Examples
Beispiel 1example 1
150 mg (0,87 mmol) 2-Difluormethyl-benzoesäure, 139 mg (0,73 mmol) 2-(l,3,3-Trimethyl-butyl)- phenylamin, 188 mg (1,45 mmol) N,N-Diisopropylethylamin und 508 mg (1,09 mmol) Brom- tripyrrolidinophosphonium-hexafluorophosphat wurden in 8 ml Acetonitril 18 h bei Raumtemperatur gerührt. Das Gemisch wurde mit 10 ml Essigsäureethylester/Wasser 1:1 versetzt, die organische Phase abgetrennt und mit 10 ml gesättigter Ammoniumchlorid-Lösung und anschließend mit 10 ml Wasser gewaschen. Abtrennen, Einengen und Trocknen der organischen Phase lieferte 810 mg Rohprodukt. Nach säulenchromatographischer Reinigung über Kieselgel 60 mit Petrolether/Essig- säureethylester-Gemisch 10:1 bis Essigsäureethylester wurden 250 mg (97,9 % der Theorie) an 2- Difluorme l-N-[2-(l,3,3-trimethyl-butyl)-phenyl]-benzamid [logP (pH 2,3) = 4,38] erhalten.150 mg (0.87 mmol) 2-difluoromethyl-benzoic acid, 139 mg (0.73 mmol) 2- (l, 3,3-trimethyl-butyl) phenylamine, 188 mg (1.45 mmol) N, N- Diisopropylethylamine and 508 mg (1.09 mmol) bromotripyrrolidinophosphonium hexafluorophosphate were stirred in 8 ml acetonitrile at room temperature for 18 h. The mixture was mixed with 10 ml of ethyl acetate / water 1: 1, the organic phase separated and washed with 10 ml of saturated ammonium chloride solution and then with 10 ml of water. Separation, concentration and drying of the organic phase gave 810 mg of crude product. After purification by column chromatography on silica gel 60 with petroleum ether / ethyl acetate mixture 10: 1 to ethyl acetate, 250 mg (97.9% of theory) of 2-difluoromene lN- [2- (1,3,3-trimethyl-butyl) -phenyl] -benzamide [logP (pH 2.3) = 4.38].
Analog Beispiel 1, sowie entsprechend den Angaben in der allgemeinen Beschreibung der erfindungsgemäßen Herstellverfahren (a) bis (i) wurden auch die in der nachstehenden Tabelle 1 genannten Verbindungen der Formel (I) erhalten:Analogously to Example 1, and in accordance with the information in the general description of the preparation processes (a) to (i) according to the invention, the compounds of the formula (I) listed in Table 1 below were also obtained:
Tabelle 1Table 1
Herstellung der Ausgangsstoffe der Formel HD Production of the starting materials of the formula HD
Beispiel (H-l)Example (H-l)
Schritt 1: Step 1:
Zu einer Lösung von 45,0 g (343 mmol) 2-Formyl-benzonitril in 500 mL Dichlormethan wurde unter Rühren eine Lösung von 47,6 mL of DAST ([Diethylaminojsulfur trifluorid) in 50 mL Dichlormethan innerhalb von 2 Stunden bei Raumtemperatur getropft. Das Reaktionsgemisch wurde für 16 Stundengerührt. Zur Aufarbeitung wurde das Lösungsmittel abgedampft und der Rückstand chromatographiert. Man erhielt 29,3 g (56 % der Theorie) an 2-Difluormethyl-benzonitril als gelbes Öl (Massenspektrometrie: [M+l] = 154).A solution of 47.6 mL of DAST ([Diethylaminojsulfur trifluoride) in 50 mL dichloromethane was added dropwise to a solution of 45.0 g (343 mmol) of 2-formyl-benzonitrile in 500 mL dichloromethane with stirring over 2 hours at room temperature. The reaction mixture was stirred for 16 hours. For working up, the solvent was evaporated and the residue was chromatographed. 29.3 g (56% of theory) of 2-difluoromethyl-benzonitrile were obtained as a yellow oil (mass spectrometry: [M + l] = 154).
Schritt 2: Eine Lösung von 29,0 g (189 mmol) 2-Difluormethyl-benzonitril in 700 mL 4%iger Natronlauge wurde 6 Stunden unter Rückfluss erhitzt. Das Reaktionsgemisch wurde auf Raumtemperatur abgekühlt, auf Eis gegossen und mit konzentrierter Salzsäure angesäuert. Der Niederschlag wurde abgesaugt und getrocknet. Man erhielt 19,3 g (58 % der Theorie) an 2-Difluormethyl-benzoesäure inStep 2: A solution of 29.0 g (189 mmol) of 2-difluoromethyl-benzonitrile in 700 mL 4% sodium hydroxide solution was heated under reflux for 6 hours. The reaction mixture was cooled to room temperature, poured onto ice and acidified with concentrated hydrochloric acid. The precipitate was filtered off and dried. 19.3 g (58% of theory) of 2-difluoromethylbenzoic acid were obtained in
Form eines weißen Feststoffes (Massenspektrometrie: [M+l] = 173).Form of a white solid (mass spectrometry: [M + l] = 173).
Die Bestimmung der angegebenen logP-Werte erfolgte gemäß EEC-Directive 79/831 Annex V.A8 durch HPLC (High Performance Liquid Chromatography) an einer Phasenumkehrsäule (C 18).The specified logP values were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a phase reversal column (C 18).
Temperatur: 43°C.Temperature: 43 ° C.
Eluenten für die Bestimmung im sauren Bereich (pH 2,3): 0,1 % wässrige Phosphorsäure, Aceto- nitril; linearer Gradient von 10 % Acetonitril bis 90 % Acetonitril.Eluents for determination in the acidic range (pH 2.3): 0.1% aqueous phosphoric acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile.
Die Eichung erfolgte mit unverzweigten Alkan-2-onen (mit 3 bis 16 Kohlenstoffatomen), derenThe calibration was carried out with unbranched alkan-2-ones (with 3 to 16 carbon atoms), the
LogP-Werte bekannt sind (Bestimmung der LogP-Werte anhand der Retentionszeiten durch lineareLogP values are known (determination of the LogP values based on the retention times by linear
Meφolation zwischen zwei aufeinanderfolgenden Alkanonen).Measurement between two successive alkanones).
Die lambda-max- Werte wurden an Hand der UV-Spektren von 200 nm bis 400 nm in den Maxima der chromatographischen Signale ermittelt. AnwendungsbeispieleThe lambda max values were determined on the basis of the UV spectra from 200 nm to 400 nm in the maxima of the chromatographic signals. applications
Beispiel AExample A
Botrytis - Test (Bohne) / protektivBotrytis test (bean) / protective
Lösungsmittel : 24,5 Gewichtsteile AcetonSolvent: 24.5 parts by weight of acetone
24,5 Gewichtsteile Dimethylacetamid Emulgator : 1 Gewichtsteil Alkyl-Aryl-Polyglykolether24.5 parts by weight of dimethylacetamide emulsifier: 1 part by weight of alkyl aryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
Zur Prüfung auf protektive Wirksamkeit werden junge Pflanzen mit der Wirkstoffzubereitung in der angegebenen Aufwandmenge besprüht. Nach Antrocknen des Spritzbelages werden auf jedes Blatt 2 kleine mit Botrytis cinerea bewachsene Agarstückchen aufgelegt. Die inokulierten Pflanzen werden in einer abgedunkelten Kammer bei ca. 20°C und 100 % relativer Luftfeuchtigkeit aufgestellt.To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on, 2 small pieces of agar covered with botrytis cinerea are placed on each leaf. The inoculated plants are placed in a darkened chamber at approx. 20 ° C and 100% relative humidity.
2 Tage nach der Inokulation wird die Größe der Befallsflecken auf den Blättern ausgewertet. Dabei bedeutet 0 % ein Wirkungsgrad, der demjenigen der Kontrolle entspricht, während ein Wirkungsgrad von 100 % bedeutet, dass kein Befall beobachtet wird.2 days after the inoculation, the size of the infection spots on the leaves is evaluated. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.
In diesem Test zeigen z.B. die Verbindungen Nr. 3 und 4 der Herstellungsbeispiele (vgl. Tabelle 1) bei einer Aufwandmenge von 500 g/ha einen Wirkungsgrad von 95 % oder besser. In this test, for example, compounds 3 and 4 of the preparation examples (cf. Table 1) show an efficiency of 95% or better at an application rate of 500 g / ha.
Beispiel BExample B
Puccinia-Test (Weizen) / protektivPuccinia test (wheat) / protective
Lösungsmittel: 25 Gewichtsteile N,N-DimethylacetamidSolvent: 25 parts by weight of N, N-dimethylacetamide
Emulgator: 0,6 Gewichtsteile AlkylarylpolyglykoletherEmulsifier: 0.6 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
Zur Prüfung auf protektive Wirksamkeit werden junge Pflanzen mit der Wirkstoffzubereitung in der angegebenen Aufwandmenge besprüht. Nach Antrocknen des Spritzbelages werden die Pflanzen mit einer Konidiensuspension von Puccinia recondita besprüht. Die Pflanzen verbleiben 48 Stunden bei 20°C und 100 % relativer Luftfeuchtigkeit in einer Inkubationskabine.To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on, the plants are sprayed with a conidia suspension of Puccinia recondita. The plants remain in an incubation cabin at 20 ° C. and 100% relative atmospheric humidity for 48 hours.
Die Pflanzen werden dann in einem Gewächshaus bei einer Temperatur von ca. 20°C und einer relativen Luftfeuchtigkeit von 80 % aufgestellt, um die Entwicklung von Rostpusteln zu begünstigen.The plants are then placed in a greenhouse at a temperature of approximately 20.degree. C. and a relative atmospheric humidity of 80% in order to promote the development of rust pustules.
10 Tage nach der Inokulation erfolgt die Auswertung. Dabei bedeutet 0 % ein Wirkungsgrad, der demjenigen der Kontrolle entspricht, während ein Wirkungsgrad von 100 % bedeutet, dass kein Befall beobachtet wird.Evaluation is carried out 10 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.
In diesem Test zeigen z.B. die Verbindung Nr. 5 der Herstellungsbeispiele (vgl. Tabelle 1) bei einer Aufwandmenge von 500 g/ha einen Wirkungsgrad von 100 %. In this test, for example, compound no. 5 of the preparation examples (cf. Table 1) show an efficiency of 100% at an application rate of 500 g / ha.
Beispiel CExample C
Sphaerotheca-Test (Gurke) / protektivSphaerotheca test (cucumber) / protective
Lösungsmittel: 49 Gewichtsteile N, N - DimethylformamidSolvent: 49 parts by weight of N, N-dimethylformamide
Emulgator: 1 Gewichtsteil AlkylarylpolyglykoletherEmulsifier: 1 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
Zur Prüfung auf protektive Wirksamkeit bespritzt man junge Gurkenpflanzen mit der Wirkstoffzubereitung in der angegebenen Aufwandmenge. 1 Tag nach der Behandlung werden die Pflanzen mit einer Sporensuspension von Sphaerotheca fuliginea inokuliert. Anschließend werden die Pflanzen in einem Gewächshaus bei 70 % relativer Luftfeuchtigkeit und einer Temperatur von 23°C aufgestellt.To test for protective effectiveness, young cucumber plants are sprayed with the preparation of active compound in the stated application rate. 1 day after the treatment, the plants are inoculated with a spore suspension of Sphaerotheca fuliginea. The plants are then placed in a greenhouse at 70% relative atmospheric humidity and a temperature of 23 ° C.
7 Tage nach der Inokulation erfolgt die Auswertung. Dabei bedeutet 0 % ein Wirkungsgrad, der demjenigen der Kontrolle entspricht, während ein Wirkungsgrad von 100 % bedeutet, dass kein Befall beobachtet wird.Evaluation is carried out 7 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.
In diesem Test zeigen z.B. die Verbindungen Nr. 3 und 5 der Herstellungsbeispiele (vgl. Tabelle 1) bei einer Aufwandmenge von 750 g/ha einen Wirkungsgrad von 100 %, die Verbindung Nr. 4 von 95 %. In this test e.g. the compounds No. 3 and 5 of the production examples (cf. Table 1) at an application rate of 750 g / ha an efficiency of 100%, the compound No. 4 of 95%.

Claims

Patentansprücheclaims
1. Difluormethylbenzanilide der Formel (I)1. difluoromethylbenzanilides of the formula (I)
in welcher in which
R1, R2, R3 und R4 unabhängig voneinander für Wasserstoff, Fluor, Chlor, Methyl, iso-Propyl oder Methylthio stehen, R5 für Wasserstoff, -Cg-Alkyl, CrC6-Alkylsulfιnyl, d-C6-Alkylsulfonyl, C C4-Alk- oxy-Cι-C -alkyl, C3-C8-Cycloalkyl; Cι-C6-Halogenalkyl, CrC4-Halogenalkylthio, Cι-C4-Halogenalkylsulfinyl, C C4-Halogenalkylsulfonyl, Halogen-Cι-C4-alkoxy-Cι-R 1 , R 2 , R 3 and R 4 independently of one another are hydrogen, fluorine, chlorine, methyl, isopropyl or methylthio, R 5 is hydrogen, -Cg-alkyl, C r C 6 -alkylsulfionyl, dC 6 -alkylsulfonyl , CC 4 alkoxy-C 1 -C 4 -alkyl, C 3 -C 8 -cycloalkyl; -C-C 6 -haloalkyl, C r C 4 -haloalkylthio, Cι-C 4 -haloalkylsulfinyl, CC 4 -haloalkylsulfonyl, halogen-Cι-C 4 -alkoxy-Cι-
Q-alkyl, C3-C8-Halogencycloalkyl mit jeweils 1 bis 9 Fluor-, Chlor- und/oder Bromatomen, Formyl-d-C3-alkyl, (d-C3-Alkyl)carbonyl-C C3-alkyl, (Cι-C3-Alkoxy carbonyl-Cι-C3-alkyl; (Cι-C3-Halogenalkyl)carbonyl-Cι-C3-alkyl, (Cι-C3-Halogen- alkoxy)carbonyl-Cι-C3-alkyl mit jeweils 1 bis 7 Fluor-, Chlor- und/oder Bromato- men, (Cι-C3-Alkyl)carbonyl-CrC3-halogenalkyl, (Cι-C3-Alkoxy)carbonyl-Cι-C3-ha- logenalkyl mit jeweils 1 bis 6 Fluor-, Chlor- und/oder Bromatomen, (CrC3-Halogen- alkyl)carbonyl-Cι -C3-halogenalkyl, (d -C3-Halogenalkoxy)carbonyl-Cι -C3-halogen- alkyl mit jeweils 1 bis 13 Fluor-, Chlor- und/oder Bromatomen; -COR6, -CONR7R8 oder -CH2NR9R10 steht, R6 für Wasserstoff, C,-C8-Alkyl, Cι-C8-Alkoxy, C C4-Alkoxy-d-C4-alkyl, C3-C8-Q-alkyl, C 3 -C 8 halocycloalkyl each having 1 to 9 fluorine, chlorine and / or bromine atoms, formyl-dC 3 -alkyl, (dC 3 -alkyl) carbonyl-C C 3 -alkyl, (Cι- C 3 alkoxy carbonyl -C 3 C 3 alkyl; (C 3 C 3 haloalkyl) carbonyl C 3 C 3 alkyl, (C 3 C 3 halo alkoxy) carbonyl C 3 C 3 alkyl each with 1 to 7 fluorine, chlorine and / or bromine, (-C-C 3 alkyl) carbonyl-C r C 3 -haloalkyl, (-C-C 3 alkoxy) carbonyl-Cι-C 3 haloalkyl each with 1 to 6 fluorine, chlorine and / or bromine atoms, (C r C 3 halogen alkyl) carbonyl -C 3 -C 3 haloalkyl, (d -C 3 haloalkoxy) carbonyl -C 3 -C 3 halogen - Alkyl with 1 to 13 fluorine, chlorine and / or bromine atoms each; -COR 6 , -CONR 7 R 8 or -CH 2 NR 9 R 10 , R 6 represents hydrogen, C, -C 8 alkyl, Cι -C 8 alkoxy, CC 4 alkoxy-dC 4 alkyl, C 3 -C 8 -
Cycloalkyl; Cι-C6-Halogenalkyl, C C6-Halogenalkoxy, Halogen-C C4-alkoxy-Cι- C4-alkyl, C3-C8-Halogencycloalkyl mit jeweils 1 bis 9 Fluor-, Chlor- und/oder Bromatomen; -COR11 steht, R7 und R8 unabhängig voneinander für Wasserstoff, CrC8-Alkyl, C C -Alkoxy-Cι-C -alkyl, d-d-Cycloalkyl; C C8-Halogenalkyl, Halogen-C C4-alkoxy-CrC4-alkyl, C3-C8-cycloalkyl; -C-C 6 haloalkyl, CC 6 -haloalkoxy, halogen-C C 4 -alkoxy-Cι- C 4 alkyl, C 3 -C 8 halocycloalkyl, each with 1 to 9 fluorine, chlorine and / or bromine atoms; -COR 11 , R 7 and R 8 independently of one another are hydrogen, C r C 8 alkyl, CC alkoxy -CC-C alkyl, dd-cycloalkyl; CC 8 -haloalkyl, halo-C C 4 -alkoxy-C r C 4 -alkyl, C 3 -C 8 -
Halogencycloalkyl mit jeweils 1 bis 9 Fluor-, Chlor- und/oder Bromatomen stehen, R7 und R8 außerdem gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, einen gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Halogen oder Q- C4-Alkyl substituierten gesättigten Heterocyclus mit 5 bis 8 Ringatomen bilden, wobei der Heterocyclus 1 oder 2 weitere, nicht benachbarte Heteroatome aus derHalogencycloalkyl are each with 1 to 9 fluorine, chlorine and / or bromine atoms, R 7 and R 8 also together with the nitrogen atom to which they are attached, optionally one or more, the same or different by halogen or Q-C 4 -Alkyl-substituted saturated heterocycle having 5 to 8 ring atoms, the heterocycle 1 or 2 further, non-adjacent heteroatoms from the
Reihe Sauerstoff, Schwefel oder NR12 enthalten kann, R9 und R10 unabhängig voneinander für Wasserstoff, d-C8-Alkyl, C3-C8-Cycloalkyl; d-C8- Halogenalkyl, C3-C8-Halogencycloalkyl mit jeweils 1 bis 9 Fluor-, Chlor- und/oderSeries can contain oxygen, sulfur or NR 12 , R 9 and R 10 independently of one another for hydrogen, dC 8 alkyl, C 3 -C 8 cycloalkyl; dC 8 - Haloalkyl, C 3 -C 8 halocycloalkyl, each with 1 to 9 fluorine, chlorine and / or
Bromatomen stehen, R9 und R10 außerdem gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, einen gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Halogen oder C C4-Alkyl substituierten gesättigten Heterocyclus mit 5 bis 8 Ringatomen bilden, wobei der Heterocyclus 1 oder 2 weitere, nicht benachbarte Heteroatome aus derAre bromine atoms, R 9 and R 10 together with the nitrogen atom to which they are attached form an optionally mono- or polysubstituted, identical or different, halogen or CC 4 alkyl-substituted saturated heterocycle with 5 to 8 ring atoms, the heterocycle 1 or 2 further, non-neighboring heteroatoms from the
Reihe Sauerstoff, Schwefel oder NR12 enthalten kann, R11 für Wasserstoff, d-C8-Alkyl, CrC8-Alkoxy, Cι-C4-Alkoxy-CrC4-alkyl, C3-C8-Series can contain oxygen, sulfur or NR 12 , R 11 for hydrogen, dC 8 alkyl, C r C 8 alkoxy, C 1 -C 4 alkoxy-C r C 4 alkyl, C 3 -C 8 -
Cycloalkyl; C C6-Halogenalkyl, CrC6-Halogenalkoxy, Halogen-Cι-C4-alkoxy-C C4-alkyl, C3-C8-Halogencycloalkyl mit jeweils 1 bis 9 Fluor-, Chlor- und/odercycloalkyl; CC 6 -haloalkyl, C r C 6 -haloalkoxy, halogen -CC-C 4 -alkoxy-C C 4 -alkyl, C 3 -C 8 -halo-cycloalkyl, each with 1 to 9 fluorine, chlorine and / or
Bromatomen steht, R12 für Wasserstoff oder C C6-Alkyl steht, Z für Z1, Z2, Z3 oder Z4 steht, worinBromine atoms, R 12 is hydrogen or CC 6 alkyl, Z is Z 1 , Z 2 , Z 3 or Z 4 , in which
Z1 für gegebenenfalls einfach bis fünffach, gleich oder verschieden substituiertes Phenyl steht,Z 1 represents phenyl which is monosubstituted to pentas, identical or differently substituted,
Z2 für gegebenenfalls einfach oder mehrfach, gleich oder verschieden substituiertesZ 2 for optionally mono- or polysubstituted, identically or differently substituted
Cycloalkyl oder Bicycloalkyl steht, Z3 für unsubstituiertes C2-C20-Alkyl oder für einfach oder mehrfach, gleich oder verschieden durch Halogen und/oder C3-C6-Cycloalkyl substituiertes Cι-C20-Alkyl steht, wobei der Cycloalkylteil seinerseits gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Halogen und/oder C]-C - Alkyl substituiert sein kann, Z4 für jeweils gegebenenfalls einfach oder mehrfach, gleich oder verschieden durchCycloalkyl or bicycloalkyl, Z 3 stands for unsubstituted C 2 -C 20 alkyl or for mono- or polysubstituted, identically or differently, by halogen and / or C 3 -C 6 cycloalkyl -CC 20 alkyl, the cycloalkyl part in turn optionally substituted one or more times, identically or differently by halogen and / or C] -C - alkyl, Z 4 for in each case optionally once or repeatedly, identically or differently by
Halogen und/oder C3-C6-Cycloalkyl substituiertes C2-C20-Alkenyl oder C2-C20-Halogen and / or C 3 -C 6 cycloalkyl substituted C 2 -C 20 alkenyl or C 2 -C 20 -
Alkinyl steht, wobei der Cycloalkylteil seinerseits gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Halogen und/oder Cι-C4-Alkyl substituiert sein kann, oderAlkynyl, where the cycloalkyl part in turn may be substituted, once or several times, identically or differently by halogen and / or C 1 -C 4 -alkyl, or
R1, R2 und R3 unabhängig voneinander für Wasserstoff oder Fluor stehen und Z und R4 gemeinsam mit den Kohlenstoffatomen, an die sie gebunden sind, einen gegebe- nenfalls substituierten 5- oder 6-gliedrigen carbocyclischen oder heterocyclischenR 1 , R 2 and R 3 independently of one another represent hydrogen or fluorine and Z and R 4 together with the carbon atoms to which they are attached are an optionally substituted 5- or 6-membered carbocyclic or heterocyclic
Ring bilden.Form a ring.
2. Difluormethylbenzanilide der Formel (I) gemäß Anspruch 1 , in welcher2. Difluoromethylbenzanilide of formula (I) according to claim 1, in which
R1, R2, R3 und R4 unabhängig voneinander für Wasserstoff, Fluor, Chlor oder Methyl stehen, R5 für Wasserstoff; Cι-C6-Alkyl, Cι-C4-Alkylsulfmyl, C C4-Alkylsulfonyl, d-C3-R 1 , R 2 , R 3 and R 4 independently of one another represent hydrogen, fluorine, chlorine or methyl, R 5 represents hydrogen; C 1 -C 6 alkyl, C 1 -C 4 alkylsulfmyl, CC 4 alkylsulfonyl, dC 3 -
Alkoxy-Cι-C3-alkyl, C3-C6-Cycloalkyl; Cι-C -Halogenalkyl, CrC4-Halogenalkyl- thio, CrC4-Halogenalkylsulfinyl, Cι-C4-Halogenalkylsulfonyl, Halogen-C C3- alkoxy-CrC3-alkyl, C3-C6-Halogencycloalkyl mit jeweils 1 bis 9 Fluor-, Chlor- und/oder Bromatomen, Formyl-d-C3-alkyl, (d-C3-Alkyl)carbonyl-CrC3-alkyl, (Cr C3-Alkoxy)carbonyl-CrC3-alkyl; (Cι-C3-Halogenalkyl)carbonyl-C C3-alkyl, (Cr C3-Halogenalkoxy)carbonyl-Cι-C3-alkyl mit jeweils 1 bis 7 Fluor , Chlor- und/oderAlkoxy -CC 3 alkyl, C 3 -C 6 cycloalkyl; -C-C -haloalkyl, C r C 4 -haloalkyl- thio, C r C 4 -haloalkylsulfinyl, Cι-C 4 haloalkylsulfonyl, halogen-C C 3 - alkoxy-C r C 3 -alkyl, C 3 -C 6 halocycloalkyl, each with 1 to 9 fluorine, chlorine and / or bromine atoms, formyl-dC 3 -alkyl, (dC 3 -alkyl) carbonyl-CrC 3 -alkyl, (C r C 3 -alkoxy) carbonyl-C r C 3 -alkyl; (-C-C 3 haloalkyl) carbonyl-C C 3 -alkyl, (C r C 3 -haloalkoxy) carbonyl-C -C 3 -alkyl each with 1 to 7 fluorine, chlorine and / or
Bromatomen, (Cι-C3-Alkyl)carbonyl-Cι-C3-halogenalkyl, (C C3-Alkoxy)carbonyl- Cι-C3-halogenalkyl mit jeweils 1 bis 6 Fluor-, Chlor- und/ oder Bromatomen, (C C3-Halogenalkyl)carbonyl-C C3-halogenalkyl, (Cι-C3-Halogenalkoxy)carbonyl-C C3-halogenalkyl mit jeweils 1 bis 13 Fluor-, Chlor- und/ oder Bromatomen; -COR6, -CONR7R8 oder -CH2NR9R10 steht,Bromine atoms, (-CC 3 alkyl) carbonyl -CC 3 -haloalkyl, (CC 3 -alkoxy) carbonyl -CC 3 -haloalkyl, each with 1 to 6 fluorine, chlorine and / or bromine atoms, (CC 3 -haloalkyl) carbonyl-C 3 -haloalkyl, (-C-C 3 -haloalkoxy) carbonyl-C 3 -haloalkyl each having 1 to 13 fluorine, chlorine and / or bromine atoms; -COR 6 , -CONR 7 R 8 or -CH 2 NR 9 R 10 ,
R6 für Wasserstoff, CrC6-Alkyl, Cι-C4-Alkoxy, d-C3-Alkoxy-d-C3-alkyl, C3-C6- Cycloalkyl; C C4-Halogenalkyl, C C4-Halogenalkoxy, Halogen-CrC3-alkoxy-Cr C3-alkyl, C3-C6-Halogencycloalkyl mit jeweils 1 bis 9 Fluor-, Chlor- und/oder Bromatomen, -COR11 steht, R7 und R8 unabhängig voneinander für Wasserstoff, d-C6-Alkyl, Cι-C3-Alkoxy-CrC3-alkyl,R 6 for hydrogen, C r C 6 alkyl, C 1 -C 4 alkoxy, dC 3 alkoxy-dC 3 alkyl, C 3 -C 6 cycloalkyl; CC 4 -haloalkyl, CC 4 -haloalkoxy, halogen-C r C 3 -alkoxy-C r C 3 -alkyl, C 3 -C 6 -halogenocycloalkyl, each with 1 to 9 fluorine, chlorine and / or bromine atoms, -COR 11 , R 7 and R 8 independently of one another are hydrogen, dC 6 -alkyl, C 1 -C 3 -alkoxy-C r C 3 -alkyl,
C3-C6-Cycloalkyl; CrC4-Halogenalkyl, Halogen-C C3-alkoxy-d-C3-alkyl, C3-C6-C 3 -C 6 cycloalkyl; C r C 4 haloalkyl, halo-C C 3 alkoxy-dC 3 alkyl, C 3 -C 6 -
Halogencycloalkyl mit jeweils 1 bis 9 Fluor-, Chlor- und oder Bromatomen stehen,Halogencycloalkyl are each with 1 to 9 fluorine, chlorine and or bromine atoms,
R9 und R10 unabhängig voneinander für Wasserstoff, Cι-C6-Alkyl, C3-C6-Cycloalkyl; C C4-R 9 and R 10 independently of one another for hydrogen, -CC 6 alkyl, C 3 -C 6 cycloalkyl; CC 4 -
Halogenalkyl, C3-C6-Halogencycloalkyl mit jeweils 1 bis 9 Fluor-, Chlor- und/oder Bromatomen stehen,Haloalkyl, C 3 -C 6 halocycloalkyl each having 1 to 9 fluorine, chlorine and / or bromine atoms,
R11 für Wasserstoff, C C6-Alkyl, d-C4-Alkoxy, Cι-C3-Alkoxy-d-C3-alkyl, C3-C6- Cycloalkyl; Cι-C4-Halogenalkyl, Cι-C4-Halogenalkoxy, Halogen-Cι-C3-alkoxy-C C3-alkyl, C3-C6-Halogencycloalkyl mit jeweils 1 bis 9 Fluor-, Chlor- und/oder Bromatomen steht, R12 für Wasserstoff oder CrC4-Alkyl steht,R 11 for hydrogen, CC 6 -alkyl, dC 4 -alkoxy, -C-C 3 -alkoxy-dC 3 -alkyl, C 3 -C 6 - cycloalkyl; Cι-C4-haloalkyl, Cι-C4-haloalkoxy, halo-Cι-C3-alkoxy-C C 3 alkyl, C 3 -C 6 -halocycloalkyl having in each case 1 to 9 fluorine, chlorine and / or bromine R 12 represents hydrogen or C r C 4 alkyl,
Z für Z1, Z2, Z3 oder Z4 steht, worinZ represents Z 1 , Z 2 , Z 3 or Z 4 , wherein
Z1 für gegebenenfalls einfach bis fünffach, gleich oder verschieden substituiertesZ 1 for optionally mono- to pentasubstituted, identically or differently substituted
Phenyl steht, wobei die Substituenten aus der Liste W1 ausgewählt sind, W1 für Halogen, Cyano, Nitro, Amino, Hydroxy, Formyl, Carboxyl, Carbamoyl, Thio- carbamoyl; jeweils geradkettiges oder verzweigtes Alkyl, Hydroxyalkyl, Oxoalkyl, Alkoxy, Alkoxyalkyl, Alkylthioalkyl, Dialkoxyalkyl, Alkylthio, Alkylsulfinyl oder Alkyl- sulfonyl mit jeweils 1 bis 8 Kohlenstoffatomen; jeweils geradkettiges oder verzweigtes Alkenyl oder Alkenyloxy mit jeweils 2 bis 6 Kohlenstoffatomen; jeweils geradkettiges oder verzweigtes Halogenalkyl, Halogenalkoxy, Halogenalkylthio, Halogenalkylsulfinyl oder Halogenalkylsulfonyl mit jeweils 1 bis 6 Kohlenstoffatomen und 1 bis 13 gleichen oder verschiedenen Halogenatomen; jeweils geradkettiges oder verzweigtes Halogenalkenyl oder Halogenalkenyloxy mit jeweils 2 bis 6 Kohlenstoffatomen und 1 bis 11 gleichen oder verschiedenenPhenyl is, the substituents being selected from the list W 1 , W 1 being halogen, cyano, nitro, amino, hydroxy, formyl, carboxyl, carbamoyl, thiocarbamoyl; in each case straight-chain or branched alkyl, hydroxyalkyl, oxoalkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, dialkoxyalkyl, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 8 carbon atoms; each straight-chain or branched alkenyl or alkenyloxy each having 2 to 6 carbon atoms; each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms; each straight-chain or branched haloalkenyl or haloalkenyloxy each having 2 to 6 carbon atoms and 1 to 11 identical or different
Halogenatomen; jeweils geradkettiges oder verzweigtes Alkylamino, Dialkylamino, Alkylcarbonyl, Alkylcarbonyloxy, Alkoxycarbonyl, Alkylaminocarbonyl, Dialkylaminocarbonyl, Arylalkylaminocarbonyl, Dialkylaminocarbonyloxy mit 1 bis 6 Kohlenstoffatomen in den jeweiligen Kohlenwasserstoffketten, Alkenylcarbonyl oder Alkinylcarbonyl, mit 2 bis 6 Kohlenstoffatomen in den jeweiligen Kohlenwasserstoff ketten; Cycloalkyl oder Cycloalkyloxy mit jeweils 3 bis 6 Kohlenstoffatomen; jeweils gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Fluor, Chlor, Oxo, Methyl, Trifluormethyl oder Ethyl substituiertes, jeweils zweifach ver- knüpftes Alkylen mit 3 oder 4 Kohlenstoffatomen, Oxyalkylen mit 2 oder 3Halogen atoms; each straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, arylalkylaminocarbonyl, dialkylaminocarbonyloxy having 1 to 6 carbon atoms in the respective hydrocarbon chains, alkenylcarbonyl or alkynylcarbonyl, with 2 to 6 carbon atoms in the respective hydrocarbon; Cycloalkyl or cycloalkyloxy each having 3 to 6 carbon atoms; each optionally monosubstituted to tetrasubstituted, identically or differently, by fluorine, chlorine, oxo, methyl, trifluoromethyl or ethyl, in each case doubly linked alkylene having 3 or 4 carbon atoms, oxyalkylene having 2 or 3
Kohlenstoffatomen oder Dioxyalkylen mit 1 oder 2 Kohlenstoffatomen; oder eine Gruppierung steht, worinCarbon atoms or dioxyalkylene with 1 or 2 carbon atoms; or a grouping stands in what
Q1 für Wasserstoff, Hydroxy, Alkyl mit 1 bis 4 Kohlenstoffatomen, Halogenalkyl mit 1 bis 4 Kohlenstoffatomen und 1 bis 9 gleichen oder verschiedenen Halogenatomen oder Cycloalkyl mit 1 bis 6 Kohlenstoffatomen steht undQ 1 represents hydrogen, hydroxy, alkyl having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms or cycloalkyl having 1 to 6 carbon atoms and
Q2 für Hydroxy, Amino, Methylamino, Phenyl, Benzyl oder für jeweils gegebenenfalls durch Halogen, Cyano, Hydroxy, Alkoxy, Alkylthio, Alkylamino, Dialkylamino oder Phenyl substituiertes Alkyl oder Alkoxy mit 1 bis 4 Kohlenstoffatomen, oder für Alkenyloxy oder Alkinyloxy mit jeweils 2 bis 4 Kohlenstoffatomen steht, sowie für jeweils gegebenenfalls im Ringteil einfach bis dreifach durch Halogen, und/oder geradkettiges oder verzweigtes Alkyl oder Alkoxy mit 1 bis 4 Kohlenstoffatomen substituiertes Phenyl, Phenoxy, Phenyllthio, Benzoyl, Benzoylethenyl, Cinnamoyl, Heterocyclyl oder Phenylalkyl, Phenylalkyloxy, Phenylalkylthio, oder Heterocyclylalkyl, mit jeweils 1 bis 3 Kohlenstoffatomen in den jeweiligenQ 2 for hydroxyl, amino, methylamino, phenyl, benzyl or for alkyl or alkoxy with 1 to 4 carbon atoms optionally substituted by halogen, cyano, hydroxy, alkoxy, alkylthio, alkylamino, dialkylamino or phenyl, or for alkenyloxy or alkynyloxy each with 2 is up to 4 carbon atoms, and for phenyl, phenoxy, phenyllthio, benzoyl, benzoylethenyl, cinnamoyl, heterocyclyl or phenylalkyl, phenylalkyloxy, which is monosubstituted to trisubstituted by halogen, and / or straight-chain or branched alkyl or alkoxy with 1 to 4 carbon atoms, in each case in the ring part, Phenylalkylthio, or heterocyclylalkyl, each having 1 to 3 carbon atoms in the respective
Alkylteilen, steht, ' Z2 für gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Cι-C4-Alkyl substituiertes Cycloalkyl oder Bicycloalkyl mit jeweils 3 bis 10 Kohlenstoffatomen steht, Z3 für unsubstituiertes C2-C2o-Alkyl oder für einfach oder mehrfach, gleich oder verschieden durch Fluor, Chlor, Brom, Iod und/oder C3-C6-Cycloalkyl substituiertes Cι-C2o-Alkyl steht, wobei der Cycloalkylteil seinerseits gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Fluor, Chlor, Brom, Iod, C C -Alkyl und/oder CrC4-Halogenalkyl substituiert sein kann, steht,Is alkyl parts, ' Z 2 is optionally monosubstituted to tetrasubstituted, identically or differently, by C 1 -C 4 -alkyl-substituted cycloalkyl or bicycloalkyl each having 3 to 10 carbon atoms, Z 3 is unsubstituted C 2 -C 2 o -alkyl or is simple or multiple, identical or different, substituted by fluorine, chlorine, bromine, iodine and / or C 3 -C 6 cycloalkyl C 1 -C 2 -alkyl, where the cycloalkyl part in turn can be substituted, optionally up to four times, identically or differently, by fluorine, chlorine, bromine, iodine, CC alkyl and / or C r C 4 haloalkyl,
Z4 für jeweils gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Fluor, Chlor, Brom, Iod und/oder C3-C6-Cycloalkyl substituiertes C2-C20-Alkenyl oder C2-C2o-Alkinyl steht, wobei der Cycloalkylteil seinerseits gegebenenfalls einfach bis vierfach, gleich oder verschieden durch Fluor, Chlor, Brom, Iod, C C4-Z 4 represents in each case optionally mono- or polysubstituted, identically or differently, by fluorine, chlorine, bromine, iodine and / or C 3 -C 6 -cycloalkyl-substituted C 2 -C 20 alkenyl or C 2 -C 2 o-alkynyl, where the cycloalkyl part in turn, if appropriate, up to four times, identically or differently, by fluorine, chlorine, bromine, iodine, CC 4 -
Alkyl und/oder C C4-Halogenalkyl substituiert sein kann, steht,Alkyl and / or CC 4 -haloalkyl may be substituted,
Z und R4 auch gemeinsam mit den Kohlenstoffatomen, an die sie gebunden sind, für einen gegebenenfalls einfach bis vierfach, gleich oder verschieden substituierten 5- oder 6- gliedrigen carbocyclischen oder heterocyclischen Ring stehen.Z and R 4 together with the carbon atoms to which they are attached represent an optionally mono- to tetrasubstituted, identically or differently substituted 5- or 6-membered carbocyclic or heterocyclic ring.
3. Verfahren zum Herstellen der Difluormethylbenzanilide der Formel (I) gemäß Anspruch 1, dadurch gekennzeichnet, dass man a) Difluormethylbenzoyl-Derivate der Formel (TT)3. A process for the preparation of the difluoromethylbenzanilides of the formula (I) according to claim 1, characterized in that a) difluoromethylbenzoyl derivatives of the formula (TT)
in welcher X1 für Chlor oder Hydroxy steht, mit Anilin-Derivaten der Formel (HI) in which X 1 represents chlorine or hydroxy, with aniline derivatives of the formula (HI)
in welcher in which
R1, R2, R3, R4, R5 und Z die in Anspruch 1 angegebenen Bedeutungen haben, gegebenenfalls in Gegenwart eines Katalysators, gegebenenfalls in Gegenwart eines Kondensationsmittels, gegebenenfalls in Gegenwart eines Säurebindemittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder b) Halogen-difluormethylbenzanilide der Formel (TV)R 1 , R 2 , R 3 , R 4 , R 5 and Z have the meanings given in claim 1, if appropriate in the presence of a catalyst, if appropriate in the presence of a condensing agent, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or b) halodifluoromethylbenzanilides of the formula (TV)
in welcher R1, R2, R3, R4 und R5 die in Anspruch 1 angegebenen Bedeutungen haben, in which R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given in Claim 1,
X2 für Chlor, Brom, Iod oder Trifluormethylsulfonat steht, mit Boronsäure-Derivaten der Formel (V)X 2 represents chlorine, bromine, iodine or trifluoromethyl sulfonate, with boronic acid derivatives of the formula (V)
in welcher in which
Z1 die in Anspruch 1 angegebene Bedeutung hat und A1 und A2 jeweils für Wasserstoff oder zusammen für Tetramethylethylen stehen, in Gegenwart eines Katalysators, gegebenenfalls in Gegenwart eines Säurebindemittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder c) Difluormethylbenzamid-Boronsäure-Derivate der Formel (VI)Z 1 has the meaning given in claim 1 and A 1 and A 2 each represent hydrogen or together represent tetramethylethylene, in the presence of a catalyst, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or c) difluoromethylbenzamide-boronic acid derivatives of the formula (VI)
in welcher in which
R1, R2, R3, R4 und R5 die in Anspruch 1 angegebenen Bedeutungen haben, A3 und A4 jeweils für Wasserstoff oder zusammen für Tetramethylethylen stehen, mit Phenyl-Derivaten der Formel (VH)R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given in Claim 1, A 3 and A 4 each represent hydrogen or together represent tetramethylethylene, with phenyl derivatives of the formula (VH)
X3— Z1 (VH) in welcherX 3 - Z 1 (VH) in which
Z1 die in Anspruch 1 angegebenen Bedeutungen hat undZ 1 has the meanings given in claim 1 and
X3 für Chlor, Brom, Iod oder Trifluormethylsulfonat steht, in Gegenwart eines Katalysators, gegebenenfalls in Gegenwart eines Säurebindemittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder d) Halogen-difluormethylbenzanilide der Formel (TV)X 3 represents chlorine, bromine, iodine or trifluoromethyl sulfonate, in the presence of a catalyst, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or d) halodifluoromethylbenzanilides of the formula (TV)
in welcher R1, R2, R3, R4 und R5 die in Anspruch 1 angegebenen Bedeutungen haben, X2 für Chlor, Brom, Iod oder Trifluormethylsulfonat steht, mit Phenyl-Derivaten der Formel (VH) in which R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given in Claim 1, X 2 represents chlorine, bromine, iodine or trifluoromethyl sulfonate, with phenyl derivatives of the formula (VH)
X3— Z1 (VH) in welcher Z1 die in Anspruch 1 angegebenen Bedeutungen hat undX 3 - Z 1 (VH) in which Z 1 has the meanings given in claim 1 and
X3 für Chlor, Brom, Iod oder Trifluormethylsulfonat steht, in Gegenwart eines Palladium- oder Nickel-Katalysators und in Gegenwart von 4,4,4',4',5,5,5,,5'-Octamethyl-2,2'-bis-l,3,2-dioxaborolan, gegebenenfalls in Gegenwart eines Säurebindemittels und gegebenenfalls in Gegenwart eines Verdünnungs- mittels umsetzt, oder e) Difluormethylbenzanilide der Formel (Ia)X 3 is chlorine, bromine, iodine or trifluoromethylsulfonate, in the presence of a palladium or nickel catalyst and in the presence of 4,4,4 ', 4', 5,5,5,, 5'-octamethyl-2,2 '-bis-l, 3,2-dioxaborolane, optionally in the presence of an acid binder and optionally in the presence of a diluent, or e) difluoromethylbenzanilides of the formula (Ia)
in welcher in which
R1, R2, R3, R4 und R5 die in Anspruch 1 angegebenen Bedeutungen haben X4 für jeweils gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Halogen und/oder d-Cβ-Cycloalkyl substituiertes C2-C20-Alkenyl oder C2-C20-Alkinyl steht, wobei der Cycloalkylteil seinerseits gegebenenfalls durch Halogen und/oder Cι-C4-Alkyl substituiert sein kann, gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Katalysators hydriert, oder f) Hydroxyalkyl-difluormethylbenzanilide der Formel (VIII)R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given in Claim 1, X 4 for each C 2 -C 20 - which is optionally mono- or polysubstituted, identically or differently, by halogen and / or d-Cβ-cycloalkyl - Alkenyl or C 2 -C 20 alkynyl, where the cycloalkyl part in turn can optionally be substituted by halogen and / or C 1 -C 4 alkyl, optionally hydrogenated in the presence of a diluent and optionally in the presence of a catalyst, or f) hydroxyalkyl-difluoromethylbenzanilides of the formula (VIII)
in welcher in which
R1, R2, R3, R4 und R5 die in Anspruch 1 angegebenen Bedeutungen haben, X5 für gegebenenfalls zusätzlich einfach oder mehrfach, gleich oder verschieden durch Halogen und/oder C3-C6-Cycloalkyl substituiertes d-C20- Hydroxyalkyl steht, wobei der Cycloalkylteil seinerseits gegebenenfalls durch Halogen und/oder Cι-C4- Alkyl substituiert sein kann, gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls inR 1 , R 2 , R 3 , R 4 and R 5 have the meanings given in Claim 1, X 5 for dC 20 which is optionally monosubstituted or polysubstituted, identically or differently, by halogen and / or C 3 -C 6 -cycloalkyl - Hydroxyalkyl is, the cycloalkyl part in turn may optionally be substituted by halogen and / or -CC 4 alkyl, optionally in the presence of a diluent and optionally in
Gegenwart einer Säure dehydratisiert, oder g) Halogen-difluormethylbenzanilide der Formel (TV)Dehydrated in the presence of an acid, or g) halodifluoromethylbenzanilides of the formula (TV)
in welcher in which
R1, R2, R3, R4 und R5 die in Anspruch 1 angegebenen Bedeutungen haben, X2 für Chlor, Brom, Iod oder Trifluormethylsulfonat steht, mit einem Alkin der Formel (EX)R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given in Claim 1, X 2 represents chlorine, bromine, iodine or trifluoromethyl sulfonate, with an alkyne of the formula (EX)
HC≡— A5 (IX), in welcherHC≡— A 5 (IX), in which
A5 für jeweils gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Halogen und/oder C3-C6-Cycloalkyl substituiertes C2-C]8-Alkyl steht, wobei der Cycloalkylteil seinerseits gegebenenfalls durch Halogen und/oderA 5 stands for C 2 -C ] 8 alkyl which is in each case optionally mono- or polysubstituted, identically or differently, by halogen and / or C 3 -C 6 cycloalkyl, the cycloalkyl part in turn optionally being substituted by halogen and / or
Ci-Q-Alkyl substituiert sein kann, oder einem Alken der Formel (X)Ci-Q-alkyl may be substituted, or an alkene of the formula (X)
in welcher A6, A7 und A8 unabhängig voneinander jeweils für Wasserstoff oder gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Halogen und/ oder C3-C6-Cycloallcyl substituiertes Alkyl stehen, wobei der Cycloalkylteil seinerseits gegebenenfalls durch Halogen und/oder Cι-C -Alkyl substituiert sein kann und die Gesamtzahl der Kohlenstoffatome des offenkettigen Molekülteils die Zahl 20 nicht übersteigt, gegebenenfalls in Gegenwart eines Verdünnungsmittels, gegebenenfalls in Gegenwart eines Säurebindemittels und in Gegenwart eines oder mehrerer Katalysatoren umsetzt, oder h) Ketone der Formel (XI) in welcher in which A 6 , A 7 and A 8 independently of one another each represent hydrogen or optionally mono- or polysubstituted, identically or differently, substituted by halogen and / or C 3 -C 6 -cycloallcyl, the cycloalkyl part in turn optionally by halogen and / or Cι-C alkyl can be substituted and the total number of carbon atoms in the open-chain part of the molecule does not exceed 20, optionally in the presence of a diluent, optionally in the presence of an acid binder and in the presence of one or more catalysts, or h) ketones of the formula (XI ) in which
R1, R2, R3, R4 und R5 die in Anspruch 1 angegebenen Bedeutungen haben,R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given in Claim 1,
A9 für Wasserstoff oder gegebenenfalls einfach oder mehrfach, gleich oder verschieden durch Halogen und/oder C3-C6-Cycloalkyl substituiertes C Cι8-A 9 for hydrogen or optionally singly or multiply, identically or differently, substituted by halogen and / or C 3 -C 6 cycloalkyl C 8 -C -
Alkyl steht, wobei der Cycloalkylteil seinerseits gegebenenfalls durch Halogen und/oder Cι-C4-Alkyl substituiert sein kann, mit einer Phosphorverbindung der allgemeinen Formel (XH)Alkyl, where the cycloalkyl part in turn can optionally be substituted by halogen and / or -CC 4 alkyl, with a phosphorus compound of the general formula (XH)
A10— Pχ (xπ), in welcherA 10 - P χ (xπ), in which
A10 für gegebenenfalls einfach oder mehrfach, gleich oder verschieden durchA 10 for optionally single or multiple, the same or different
Halogen und/oder C3-C6-Cycloalkyl substituiertes C Cι8-Alkyl steht, wobei der Cycloalkylteil semerseits gegebenenfalls durch Halogen und/oder d-C4-Halogen and / or C 3 -C 6 cycloalkyl-substituted C 8 -C 8 alkyl, the cycloalkyl part on the part optionally being halogen and / or dC 4 -
Alkyl substituiert sein kann, Px für eine Gruppierung -P+(C6H5)3 CT, BT, -P+(C6H5)3 T,Alkyl may be substituted, Px for a grouping -P + (C6H 5 ) 3 CT, BT, -P + (C6H 5 ) 3 T,
-P(=0)(OCH3)3 oder -P(=0)(OC2H5)3 steht, gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder Difluormethylbenzanilide der Formel (Ib)-P (= 0) (OCH 3 ) 3 or -P (= 0) (OC 2 H 5 ) 3 , optionally reacted in the presence of a diluent, or difluoromethylbenzanilides of the formula (Ib)
in welcher in which
R1, R2, R3, R4 und Z die in Anspruch 1 angegebenen Bedeutungen haben mit einem Halogenid der Formel (XHI)R 1 , R 2 , R 3 , R 4 and Z have the meanings given in Claim 1 with a halide of the formula (XHI)
in welcher R5"1 für d-C8-Alkyl, C C6-Alkylsulfmyl, CrC6-Alkylsulfonyl, C C4-Alkoxy- in which R 5 "1 for dC 8 alkyl, CC 6 alkylsulfmyl, C r C 6 alkylsulfonyl, CC 4 alkoxy-
CrC4-alkyl, C3-C8-Cycloalkyl; C,-C6-Halogenalkyl, CrC4-Halogenalkyl- thio, C C4-Halogenalkylsulfinyl, Cι-C4-Halogenalkylsulfonyl, Halogen-d- C4-alkoxy-Cι-C4-alkyl, C3-C8-Halogencycloalkyl mit jeweils 1 bis 9 Fluor-, Chlor- und/oder Bromatomen, Formyl-Cι-C3-alkyl, (C]-C3-Alkyl)carbonyl- d-C3-alkyl, (C C3-Alkoxy)carbonyl-C C3-alkyl; (d-C3-Halogenalkyl)- carbonyl-Cι-C3-alkyl, (Cι-C3-Halogenalkoxy)carbonyl-Cι-C3-alkyl mit je- weils 1 bis 7 Fluor-, Chlor- und/oder Bromatomen, (Cι-C3-Alkyl)carbonyl-C r C 4 alkyl, C 3 -C 8 cycloalkyl; C, -C 6 -haloalkyl, C r C 4 -haloalkyl-thio, CC 4 -haloalkylsulfinyl, -C-C 4 haloalkylsulfonyl, halogen-d- C 4 -alkoxy-C 4 -C 4 alkyl, C 3 -C 8 halocycloalkyl each having 1 to 9 fluorine, chlorine and / or bromine atoms, formyl C 1 -C 3 alkyl, (C] -C 3 - Alkyl) carbonyl-dC 3 -alkyl, (CC 3 -alkoxy) carbonyl-C C 3 -alkyl; (dC 3 -haloalkyl) - carbonyl-C 3 -C 3 -alkyl, (-C-C 3 -haloalkoxy) carbonyl-C 3 -C 3 -alkyl each with 1 to 7 fluorine, chlorine and / or bromine atoms, ( -C-C 3 alkyl) carbonyl
Cι-C3-halogenalkyl, (C C3-Alkoxy)carbonyl-Cι-C3-halogenalkyl mit jeweils 1 bis 6 Fluor-, Chlor- und/oder Bromatomen, (C C3-Halogenalkyl)- carbonyl-d-d-halogenalkyl, (Cι-C3-Halogenalkoxy)carbonyl-C C3-halo- genalkyl mit jeweils 1 bis 13 Fluor-, Chlor- und/oder Bromatomen; -COR6, -CONR7R8 oder -CH2NR9R10 steht,-C-C 3 haloalkyl, (CC 3 -alkoxy) carbonyl -CC -C 3 haloalkyl, each with 1 to 6 fluorine, chlorine and / or bromine atoms, (CC 3 -haloalkyl) - carbonyl-dd-haloalkyl, ( -C-C 3 -haloalkoxy) carbonyl-C C 3 -haloalkyl, each with 1 to 13 fluorine, chlorine and / or bromine atoms; -COR 6 , -CONR 7 R 8 or -CH 2 NR 9 R 10 ,
R6, R7, R8, R9 und R10 die in Anspruch 1 angegebenen Bedeutungen haben,R 6 , R 7 , R 8 , R 9 and R 10 have the meanings given in Claim 1,
X6 für Chlor, Brom oder Iod steht, in Gegenwart einer Base und in Gegenwart eines Verdünnungsmittels umsetzt.X 6 represents chlorine, bromine or iodine, in the presence of a base and in the presence of a diluent.
4. Mittel zur Bekämpfung unerwünschter Mikroorganismen, gekennzeichnet durch einen4. Means for controlling unwanted microorganisms, characterized by a
Gehalt an mindestens einem Difluormethylbenzanilid der Formel (I) gemäß Anspruch 1 neben Streckmitteln und/oder oberflächenaktiven Stoffen.Content of at least one difluoromethylbenzanilide of the formula (I) according to claim 1 in addition to extenders and / or surface-active substances.
5. Verwendung von Difluormethylbenzaniliden der Formel (I) gemäß Anspruch 1 zur Be- kämpfung unerwünschter Mikroorganismen.5. Use of difluoromethylbenzanilides of the formula (I) according to Claim 1 for combating undesired microorganisms.
6. Verfahren zur Bekämpfung unerwünschter Mikroorganismen, dadurch gekennzeichnet, dass man Difluormethylbenzanilide der Formel (I) gemäß Anspruch 1 auf die Mikroorganismen und/oder deren Lebensraum ausbringt.6. A method for controlling undesirable microorganisms, characterized in that difluoromethylbenzanilides of the formula (I) according to claim 1 are applied to the microorganisms and / or their habitat.
7. Verfahren zur Herstellung von Mitteln zur Bekämpfung unerwünschter Mikroorganismen, dadurch gekennzeichnet, dass man Difluormethylbenzanilide der Formel (I) gemäß Anspruch 1 mit Streckmitteln und/oder oberflächenaktiven Stoffen vermischt.7. A process for the preparation of agents for controlling unwanted microorganisms, characterized in that difluoromethylbenzanilides of the formula (I) according to Claim 1 are mixed with extenders and / or surface-active substances.
8. Hydroxyalkyl-difluormethylbenzanilide der Formel (VHI)8. Hydroxyalkyl difluoromethylbenzanilides of the formula (VHI)
in welcher R1, R2, R3, R und R5 die in Anspruch 1 angegebenen Bedeutungen haben und X5 für gegebenenfalls zusätzlich einfach oder mehrfach, gleich oder verschieden durch Halogen und/oder C3-C6-Cycloalkyl substituiertes C2-C20-Hydroxyalkyl steht, wobei der Cycloalkylteil seinerseits gegebenenfalls durch Halogen und/oder C C4- Alkyl substituiert sein kann. in which R 1, R 2, R 3, R and R 5 have the meanings given in claim 1 and X 5 represents optionally additionally mono- or polysubstituted by identical or different manner by halogen and / or C 3 -C 6 cycloalkyl C 2 -C 20 -hydroxyalkyl, where the cycloalkyl part in turn can optionally be substituted by halogen and / or CC 4 alkyl.
Difluormethylbenzoyl-Derivate der Formel (H)Difluoromethylbenzoyl derivatives of the formula (H)
in welcher X1 für Chlor oder Hydroxy steht. in which X 1 represents chlorine or hydroxy.
10. Verfahren zum Herstellen von Difluormethylbenzoyl-Derivaten der Formel (II) gemäß Anspruch 9, dadurch gekennzeichnet, dass man 2-Formyl-benzomtril der Formel (XIV)10. A process for the preparation of difluoromethylbenzoyl derivatives of the formula (II) according to claim 9, characterized in that 2-formylbenzometril of the formula (XIV)
in einem ersten Schritt mit (Diethylamino)schwefeltrifluorid in Gegenwart eines Verdünnungsmittels fluoriert, und das so erhaltene 2-Difluormethyl-benzomtril der Formel (XV) fluorinated in a first step with (diethylamino) sulfur trifluoride in the presence of a diluent, and the 2-difluoromethylbenzometril of the formula (XV) thus obtained
in einem zweiten Schritt mit einer Base umsetzt und diese Säure in einem dritten Schritt gegebenenfalls mit einem Chlorierungsmittel in in a second step with a base and this acid in a third step, optionally with a chlorinating agent
Gegenwart eines Verdünnungsmittels zum entsprechenden Säurechlorid umsetzt. In the presence of a diluent to the corresponding acid chloride.
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BRPI0410443A (en) 2006-05-30
AU2004240721A1 (en) 2004-12-02
JP2007502312A (en) 2007-02-08
WO2004103953A1 (en) 2004-12-02

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