WO2005063710A1 - 3-trifluoromethyl picolinic acid anilides, and use thereof as fungicides - Google Patents

3-trifluoromethyl picolinic acid anilides, and use thereof as fungicides Download PDF

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WO2005063710A1
WO2005063710A1 PCT/EP2004/014621 EP2004014621W WO2005063710A1 WO 2005063710 A1 WO2005063710 A1 WO 2005063710A1 EP 2004014621 W EP2004014621 W EP 2004014621W WO 2005063710 A1 WO2005063710 A1 WO 2005063710A1
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alkyl
halogen
alkoxy
phenyl
groups
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PCT/EP2004/014621
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German (de)
French (fr)
Inventor
Markus Gewehr
Michael Rack
Bernd Müller
Thomas Grote
Wassilios Grammenos
Jordi Tormo I Blasco
Anja Schwögler
Joachim Rheinheimer
Carsten Blettner
Peter Schäfer
Frank Schieweck
Oliver Wagner
John-Bryan Speakman
Siegfried Strathmann
Reinhard Stierl
Jan Rether
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Basf Aktiengesellschaft
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Priority to JP2006546061A priority Critical patent/JP2007534652A/en
Priority to EP04804216A priority patent/EP1699763A1/en
Publication of WO2005063710A1 publication Critical patent/WO2005063710A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/22—O-Aryl or S-Aryl esters thereof

Definitions

  • the present invention relates to 3-trifluoromethylpicolinic acid anilides with fungicidal activity and their use as fungicides, i.e. to combat harmful fungi.
  • Hetarylanilides with fungicidal activity are the subject of numerous patent applications (see, for example, WO 86/02641, JP 01313402, US 4,877,441, EP 371950, WO 93/11117, EP 545099, DE 4204766, DE 4204768, EP 591699, EP 589301, JP 07145156, JP 08092223, WO 97/08148, WO 98/03500, EP 824099, EP 846416, WO 00/09482, WO 01/42223, EP 1110454, EP 1110956, WO 01/49664, JP 2001-302605, WO 02/08195, WO 02/08197, WO 02/38542, WO 02/59086, WO 02/064562, WO 03/010149, WO 03/66609, WO 03/66610, WO 03/69995, WO 03/74491 and WO 03/70705) , The hetarylanilides described there, however
  • JP 58096069 describes fungicidally active picolinic anilides of the general formula
  • R is CH 3 or CF 3 , known.
  • R is CH 3 or CF 3
  • fungicidal activity of these compounds is unsatisfactory.
  • the present invention is therefore based on the object of providing further fungicidally active compounds which overcome the disadvantages of the compounds known from the prior art and in particular have an improved action at low application rates.
  • these compounds should have good crop tolerance and should show little or no harm to animal use if possible.
  • n 0, 1, 2, 3 or 4 and the substituents have the following meaning:
  • R 1 , R 2 , R 3 independently of one another are hydrogen, halogen, nitro, CN, CC 4 -alkyl, C 3 - C 6 -cycloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, CC 4 - Alkoxy, where the hydrogen atoms in the last 4 groups mentioned can be partially or completely substituted by halogen;
  • R 4 is hydrogen, OH, CC 4 alkyl, C 3 -C 6 cycloalkyl, -C-C 4 alkox, the
  • Hydrogen atoms in the last 3 groups mentioned can be partially or completely substituted by halogen; R 5 unsubstituted C -C 12 alkyl, C 3 -C 12 cycloalkyl, C 3 -C ⁇ 2 alkenyl, C 5 -C 12 -
  • Cycloalkenyl, C 3 -C 12 alkynyl, wherein the 5 latter groups can each have 1, 2 or 3 substituents R 9 , and wherein the hydrogen atoms in the 5 latter groups can be partially or completely substituted by halogen; C ⁇ -C ⁇ 2 -haloalkyl, C 2 C ⁇ alkyl having 1, 2 or 3 substituents R 11, a group -C (R 10) NOR 8, a group -C (O) NR 13 R 14;
  • R 7 CC 4 alkyl, C 3 -C 6 cycloalkyl, CC ⁇ alkoxy, C 2 -C 4 alkenyl, C 2 -C 4 -
  • Sulfur can be replaced and in which some or all of the hydrogen can be replaced by halogen; R 8 -C 4 alkyl, C 3 -C 6 cycloalkyl, C 2 -C alkenyl, C 2 -C 4 alkynyl, where the hydrogen atoms in these 4 groups can be partially or completely substituted by halogen,
  • R 9 C GrAlkyl, CC 8 alkoxy, C 2 -C 8 alkenyloxy, C 2 -C 8 alkynyloxy, CC 4 -
  • Alkoxy-CrCs-alkoxy where the hydrogen atoms in these groups can be partially or completely substituted by halogen;
  • R 10 is hydrogen, halogen, -CC 8 alkoxy, C 2 -C 8 alkenyloxy, C 2 -C 8 alkynyloxy,
  • Phenyl which can have 1, 2, 3 or 4 of the groups mentioned under R 7 , R 11 CC 4 alkyl, CC 8 alkoxy, d-Cs-alkoxy-C Cs-alkoxy, C 2 -C 8 -alkenoxy,
  • R 12 is hydrogen, OH, CC alkyl, CC 4 alkoxy, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl,
  • R 13 , R 14 independently of one another are hydrogen, CC 4 -alkyl, C 2 -C -alkenyl, C 2 -C 4 -alkynyl, where the hydrogen atoms in these groups can be partially or completely substituted by halogen;
  • the present invention also relates to the use of the 3-trifluoromethylpicolinic acid anilides of the general formula I and their agriculturally acceptable salts as fungicides, and to crop protection agents containing them.
  • the present invention further relates to a method for combating phytopathogenic fungi (harmful fungi), which is characterized in that the harmful fungi, their habitat or the plants, areas, materials or spaces to be kept free by them with a fungicidally effective amount of a 3- Trifluoromethylpicolinklaanilids of general formula I and / or an agriculturally acceptable salt of I treated.
  • phytopathogenic fungi harmful fungi
  • the harmful fungi their habitat or the plants, areas, materials or spaces to be kept free by them with a fungicidally effective amount of a 3- Trifluoromethylpicolinklalids of general formula I and / or an agriculturally acceptable salt of I treated.
  • the 3-trifluoromethylpicolinic acid anilides of the formula I can have one or more centers of chirality and are then present as mixtures of enantiomers or diastereomers.
  • the invention relates both to the pure enantiomers or diastereomers and to their mixtures.
  • Suitable compounds of formula I also include all possible stereoisomers (cis / trans isomers) and mixtures thereof.
  • Agriculturally useful salts include, in particular, the salts of those cations or the acid addition salts of those acids whose cations or anions do not adversely affect the fungicidal activity of the compounds I.
  • cations in particular the ions of the alkali metals, preferably sodium and potassium, the alkaline earth metals, preferably calcium, magnesium and barium, and the transition metals, preferably manganese, copper, zinc and iron, and the ammonium ion, if desired one to four CC 4 alkyl substituents and / or can carry a phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri (CC-alkyl) sulfonium and sulfoxonium ions C, preferably tri (C ⁇ -C ⁇ 4- alky
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, as well as the anions of CrC 4 -alkanoic acids, preferably formic acids, preferably formic acids, preferably Propionate and butyrate. They can be formed by reacting I with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • CC alkyl and the alkyl parts in alkoxyalkyl, alkylsulfonyl and alkylthio for: CH 3 , C 2 H 5 , CH 2 -C 2 H 5 , CH (CH 3 ) 2> n-butyl, CH (CH 3 ) -C 2 H 5 , CH -CH (CH 3 ) 2 or C (CH 3 ) 3 ;
  • CC 4 haloalkyl for a CrC ⁇ alkyl radical as mentioned above, in which the hydrogen atoms are partially, for example 1, 2 or 3, or completely by halogen such as fluorine, chlorine, bromine and / or iodine, in particular by chlorine and / or fluorine and especially are substituted by fluorine, for example CH 2 F, CHF 2 , CF 3 , CH 2 CI, CH (CI) 2 ,
  • C (CI) 3 chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2nd -Chlor-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, C 2 F 5 , 2-fluoropropyi, 3-fluoropropyI, 2,2-difluoropropyl, 2,3- Difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl,
  • CC 12 alkyl for a saturated hydrocarbon radical having 1 to 12 carbon atoms, for example for a CrC ⁇ alkyl radical as mentioned above, or for for example n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2- Dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl,
  • Double bond in any position e.g. Ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-buten-1-yl, 1-buten-2-yl, 1-buten-3-yl, 2-buten-1-yl, 1-methyl prop-1 -en-1 -yl, 2-methyl-prop-1 -en-1 -yl, 1-methyl-prop-2-en-1 -yl, 2-methyl-prop-2-en-1- yl;
  • C 2 -C 2 alkenyl unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 12 carbon atoms and a double bond in any position, for example for C 2 -C 4 alkenyl as mentioned above and z.
  • 3-methyl-pent-4-en-1-yl 4-methyl-pent-4-en-1-yl, 1, 1-dimethyl-but-2-en-1-yl, 1, 1-dimethyl but-3-en-1-yl, 1, 2-dimethyl-but-1-en-1-yl, 1, 2-dimethyl-but-2-en-1-yl, 1, 2-dimethyl-but- 3-en-1-yl, 1,3-dimethyl-but-1-en-1-yl, 1,3-dimethyl-but-2-en-1-yl, 1,3-dimethyl-but-3- en-1-yl, 2,2-dimethyl-but-3-en-1-yl,
  • C 2 -C 2 alkynyl for straight-chain or branched hydrocarbon groups having 2 to 12 carbon atoms and a triple bond in any position, for example ethynyl, prop-1-in-1-yl, prop-2-in-1-yl, n -But-1-in-1-yl, n-but-1-in-3-yl, n-but-1-in-4-yl, n-but-2-in-1-yl, n-pent -1-in-1-yl, n-pent-1-in-3-yl, n-pent-1-in-4-yl, n-pent-1-in-5-yl, n-pent-2 -in-1-yl, n-pent-2-yn-4-yI, n-pent-2-yn-5-yl, 3-methyl-but-1-yn-3-yl, 3-methyl-but -1-in-4-yl, n-hex-1-in-1-yl, n-he
  • CC 4 alkoxy for OCH 3 , OC 2 H 5 , OCH 2 -C 2 H 5 , OCH (CH 3 ) 2 , n-butoxy, OCH (CH 3 ) -C 2 H 5 , OCH 2 -CH (CH 3 ) 2 or OC (CH 3 ) 3 ;
  • CC 4 haloalkoxy for a CrC 4 alkoxy radical as mentioned above, in which a part, for example 1, 2 or 3 or all, of hydrogen atoms.
  • Halogen in particular substituted by chlorine and / or fluorine and especially by fluorine, for example OCH 2 F, OCHF 2l OCF 3 , OCH2CI, OCH (CI) 2 , OC (CI) 3) chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2 -Fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2.2 dichloro-2-fluoroethoxy,
  • 2,2,2-trichloroethoxy, OC 2 F 5 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, - 2- Bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH 2 -C 2 F 5 , OCF 2 -C 2 F 5) 1- (CH 2 F) -2-fluoroethoxy, 1- (CH 2 CI) -2-chloroethoxy, 1- (CH 2 Br) -2-bromethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy, preferably for OCHF 2 , OCF 3 , dichlorofluoromethoxy, Chlorodifluoromethoxy or 2,2,2-trifluoroeth
  • C 3 -C 6 cycloalkyl for cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
  • C 3 -Ci 2 -cycloalkyl for a mono-, bi- or tricyclic hydrocarbon radical, for example for a C 3 -C 6 -cycloalkyl radical as mentioned above or for cycloheptyl, cyclooctyl, bicyclo [2.2.1] heptyl, bicyclo [2.2.
  • Cycloalkyl-C 4 -C 4 alkyl for C 1 -C 4 alkyl which is substituted by C 3 -C 12 cycloalkyl, for example cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctyl methyl , 2- (cyclopropyl) ethyl, 2- (cyclobutyl) ethyl, 2- (cyclopentyl) ethyl, 2- (cyclohexyl) ethyl, 2- (cycloheptyl) ethyl, 2- (cyclooctyl) ethyl, 3- (cyclopropyl) propyl,
  • CC 4 -alkoxy-C C -alkyl for -C-C alkyl which is substituted by CC 4 -alkoxy, for example for methoxymethyl, ethoxymethyl, 1- or 2-methoxyethyl, 1- or 2-ethoxyethyl, 1-, 2nd - or 3-methoxypropyl;
  • dd-alkoxy which is substituted by CC 4 -alkoxy, for example for methoxymethoxy, ethoxymethoxy, 1- or 2-methoxyethoxy, 1- or 2-ethoxyethoxy, 1-, 2- or 3- methoxypropoxy;
  • Phenyl-CrC 6 -alkyl for CC 6 -alkyl which is substituted by phenyl, for example for benzyl, 1- or 2-phenylethyl, 1-, 2- or 3-phenylpropyI;
  • Phenyloxy -CC 6 alkyl for CC 6 alkyl which is substituted with phenoxy, for example for phenoxymethyl, 1- or 2-phenoxyethyl, 1-, 2- or 3-phenoxypropyl;
  • Phenyl-C 2 -C 6 -alkenyl for C 2 -C 6 -alkenyl which is substituted with phenyl, for example for 1- or 2-phenylethenyl, 1-phenylprop-2-en-1-yl, 3- Phenyl-1-propen-1-yl, 3-phenyl-2-propen-1-yl, 4-phenyl-1-buten-1-yl or 4-phenyl-2-buten-1-yl;
  • Phenyloxy-C 2 -C 6 alkenyl for C 2 -C 6 alkenyl which is substituted with phenoxy, for example for 1- or 2-phenyloxyethenyl, 1-phenyloxyprop-2-en-1-yl, 3-phenyloxy -1-propen-1-yl, 3-phenyloxy-2-propen-1-yl, 4-phenyloxy-1-buten-1-yl or 4-phenyloxy-2-buten-1-yl;
  • Phenyl-C 2 -C 6 -alkynyl for C 2 -C 6 -alkynyl which is substituted with phenyl, for example for 1-phenylprop-2-yn-1-yl, 3-phenyl-1-propyne-1- yl, 3-phenyl-2-propin-1-yl, 4- Phenyl-1-butin-1-yl or 4-phenyl-2-butin-1-yl;
  • Phenyloxy-C 2 -C 6 -alkynyl for C 2 -C 6 -alkynyl which is substituted by phenoxy, for example for 1-phenyloxyprop-2-in-1-yl, 3-phenyloxy-1-propin-1- yl, 3-phenyloxy-2-propin-1-yl, 4-phenyloxy-1-butyn-1-yl or 4-phenyloxy-2-butyn-1-yl.
  • anilides of the general formula I are preferred in which the variables R 1 to R 6 have the following meanings independently of one another and in particular in combination:
  • R 1 , R 2 , R 3 independently of one another are hydrogen, halogen, CC 4 -alkyl or CC 4 - haloalkyl.
  • 1, 2 or preferably all of the radicals R 1 , R 2 and R 3 are hydrogen;
  • R 4 is hydrogen, methyl, OH or methoxy, especially hydrogen
  • R 5 has one of the following meanings:
  • CrC 12 haloalkyl in particular CC 4 fluoroalkyl, Crd-alkoxy-Cr C 4 alkyl, Crd-haloalkoxy-Crd alkyl, in particular CC 4 - fluoroalkoxy-C C 4 alkyl;
  • Alkyl group can be partially, for example 1-, 2- or 3-fold or completely substituted by halogen; and R 6 independently of one another: CC 4 -alkyl, CC 4 -alkoxy, CC -haloalkyl,
  • CrC 4 haloalkoxy, or halogen especially fluorine, chlorine, methyl, trifluoromethyl, methoxy, trifluoromethoxy or difluoromethyl.
  • variable R 7 is selected in particular from 4 alkyl CC, CC 4 -alkoxy, CC 4 - haloalkyl, CC 4 -haloalkoxy, nitro, CN or halogen, especially fluorine, chlorine, methyl, trifluoromethyl, methoxy, trifluoromethoxy or difluoromethyl.
  • the variable R 8 is preferably selected from CC 4 alkyl, C 3 -C 6 cycloalkyl, CC 4 alkoxy, C 2 -C 4 alkenyl, C 2 -C alkynyl, the hydrogen atoms in these 5 groups being partially or may be completely substituted by halogen, halogen, nitro, CN, phenyl which may have 1, 2, 3 or 4 of the groups mentioned under R 6 , phenoxy which may have 1, 2, 3 or 4 of the groups mentioned under R 6 , d-Ce-alkylphenyl, where the hydrogen atoms of the alkyl part can be partially or completely substituted by halogen and the phenyl ring can have 1, 2, 3 or 4 of the groups mentioned under R 6 , in particular under CC 4 alkyl, C 3 -C 6 cycloalkyl, C 2 -C alkenyl, C 2 -C 4 alkynyl, where the hydrogen atoms in these 4 groups can be partially or completely substituted by
  • variable W stands in particular for oxygen.
  • X in formula I represents a direct bond or oxygen.
  • X stands for oxygen.
  • X stands for a direct bond. If R 5 is unsubstituted alkyl, X is in particular a direct bond.
  • those anilides of the formula I are preferred in which the group XR 5 is bonded in the ortho or meta position and in particular in the ortho position to the amide nitrogen.
  • those anilides in which R 5 has one of the following meanings are particularly preferred.
  • -C-C 12 haloalkyl in particular CC 4 fluoroalkyl, dC 4 alkoxy-dC alkyl, CC 4 haloalkoxy-C r C 4 alkyl, especially CC 4 fluoroalkoxy C C alkyl;
  • -C (CrC 4 alkyl) NO-R 8 , where the hydrogen atoms of the dC 4 alkyl group can be partially or completely substituted by halogen.
  • R 7 and R 8 have in particular the meanings given as preferred, W in particular represents oxygen.
  • Activated carboxylic acid derivatives are, for example, halides, active esters, anhydrides, azides, for example chlorides, fluorides, bromides, para-nitrophenyl esters, pentafluorophenyl esters , N-hydroxysuccinimide ester and hydroxybenzotriazol-1-yl ester.
  • L represents a suitable nucleophilically displaceable leaving group, for example halide, active ester residue, an anhydride residue, azide, for example chloride, fluoride, bromide, para-nitrophenyloxy, pentafluorophenyloxy, one of N-hydroxysuccinimide or of hydroxybenzotriazole-1 -yl derived rest.
  • the 3-trifluoromethylpicolinic acid anilides of the general formula I can also be prepared by reacting the free acids IIIa with an optionally N-substituted aniline purple in the presence of a coupling reagent (Scheme 2).
  • Coupling reagents can be, for example:
  • Coupling reagents that form mixed anhydrides with carbonic acid esters e.g. 2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline [B. Belleau, G. Malek, J. Amer. Chem. Soc. 1968, 90, 1651.], 2-iso-butyloxy-1-iso-butyloxycarbonyl-1, 2-dihydroquinoline [Y. Kiso, H. Yajima, J. Chem. Soc, Chem. Commun. 1972, 942.];
  • Phosphonium-based coupling reagents e.g. (BenzotriazoM-yloxy) tris- (dimethylamino) -phosphonium hexafluorophosphate [B. Castro, J.R. Domoy, G. Evin, C. Selve, Tetrahedron Lett. 1975, 14, 1219.], (Benzotriazol-1-yloxy) - tripyrrolidinophosphonium hexafluorophosphate [J. Coste et.al., Tetrahedron Lett. 1990, 31, 205.];
  • Coupling reagents based on uronium or with guanidinium N-oxide structure e.g. N, N, N ', N'-tetramethyl-O- (1H-benzotriazol-1-yl) uronium hexafluorophosphate [R. Knorr, A. Trzeciak, W. Bannwarth, D. Gillessen, Tetrahedron Lett. 1989, 30, 1927.]
  • N, N, N ', N'-tetramethyl-O- (benzotriazol-1-yl) uronium tetrafluoroborate, (benzotriazol-l-yloxy) dipiperidinocarbenium hexafluorophosphate e.g. N, N, N ', N'-tetramethyl-O- (1H-benzotriazol-1-yl) uronium hexafluorophosphate [R. Knorr, A. Trzeciak, W. Bann
  • Coupling reagents that form acid chlorides e.g. Phosphoric acid bis (2-oxo-oxazo! Idid) chloride [J. Diago-Mesequer, Synthesis 1980, 547.].
  • the 3-trifluoromethylpicolinic acids IIIa can be prepared by methods known from the literature, e.g. from the corresponding pyridine-2,3-dicarboxylic acids by reaction with sulfur tetrafluoride based on that described in J. Fluorine Chem. 1993, 60, pp. 233-237; JP 1980-5059135; US 4803205; or khim. Geterotsikl. Soedin 1994, pp. 657-659; or by introducing the carboxyl group according to the in Eur. J. Org. Chem. 2002, pp. 327-330.
  • the activated thiophenecarboxylic acid derivatives II can be synthesized therefrom by methods known from the literature [Houben-Weyl: “Methods of organ. Chemistry ", Georg Thieme Verlag, Stuttgart, New York 1985, Volume E5, pp. 587-614, 633-772.]
  • the 3-trifluoromethylpicolinic acid anilides of the general formula I and their agriculturally compatible, i.e. usable salts are suitable as fungicides. They are characterized by excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some of them are systemically effective and can be used in plant protection as leaf and soil fungicides.
  • Botrytis cinerea • aging aria types of vegetables and fruits, Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and vines,
  • Rhizoctonia species on cotton, rice and lawn are Rhizoctonia species on cotton, rice and lawn.
  • Venturia species scab on apples and pears.
  • the compounds of the formula I are also suitable for combating harmful fungi such as Paecilomyces variotii in the protection of materials (e.g. wood, paper, dispersions for painting, fibers or fabrics) and in the protection of stored products.
  • harmful fungi such as Paecilomyces variotii in the protection of materials (e.g. wood, paper, dispersions for painting, fibers or fabrics) and in the protection of stored products.
  • the compounds of the formula I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally active amount of the active compounds.
  • the application can take place both before and after the infection of the materials, plants or seeds by the fungi.
  • the fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active ingredient.
  • the application rates in crop protection are between 0.01 and 2.0 kg of active ingredient per ha.
  • active ingredient 0.001 to 0.1 g, preferably 0.01 to 0.05 g, per kg of seed are generally required.
  • the amount of active ingredient applied depends on the type of application and the desired effect. Usual application rates in material protection are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active ingredient per cubic meter of treated material.
  • the compounds of formula I can be converted into the usual formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the form of application depends on the respective purpose; in any case, it should ensure a fine and uniform distribution of the compound according to the invention.
  • the formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, where in the case of water as diluent other organic solvents can also be used as auxiliary solvents.
  • auxiliaries solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g.
  • Carriers such as natural powdered rock (e.g. kaolins, clays, talc, chalk) and synthetic powdered rock (e.g. highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste liquors and methyl cellulose.
  • Carriers such as natural powdered rock (e.g. kaolins, clays, talc, chalk) and synthetic powdered rock (e.g. highly disperse silica, silicates)
  • Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste
  • Suitable surfactants are alkali metal, alkaline earth metal salts, sulfonic acid ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids and their alkali and alkaline earth metal salts, salts of sulfated fatty alcohol glycol ethers, condensates of sulfonated naphthalene and naphthalene derivatives with Formaldehyde, condensation products of naphthalene or naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphe- nol, octylphenol, nonyl
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • Granules e.g. Coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid carriers.
  • Solid carriers are e.g. Mineral soils, such as silica gel, silicas, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.
  • Mineral soils such as silica gel, silicas, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomi
  • the formulations generally contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight, of the active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • V. 80 parts by weight of a compound according to the invention are mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite liquor and 7 parts by weight.
  • the stock solution is then diluted to the desired concentration, e.g. to a concentration in the range of 1 to 100 ppm.
  • the active ingredients as such in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, old dispersions, pastes, dusts, sprinkling agents, granules by spraying, atomizing, dusting, scattering or pouring.
  • the application forms depend entirely on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, old dispersions) by adding water.
  • emulsions, pastes or old dispersions the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • concentrates consisting of an active substance, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or oil can also be prepared which are suitable for dilution with water.
  • the active ingredient concentrations in the ready-to-use preparations can be varied over a wide range. Generally they are between 0.0001 and 10%. Small amounts of active compound I are often sufficient in the ready-to-use preparation, e.g. 2 to 200 ppm. Ready-to-use preparations with active ingredient concentrations in the range from 0.01 to 1% are also preferred. •
  • the active ingredients can also be used with great success in the ultra-low-volume process (ULV), it being possible to apply formulations with more than 95% by weight of active ingredient or even the active ingredient without additives.
  • UUV ultra-low-volume process
  • the active substances can include oils of various types, herbicides, fungicides, and others. Pesticides, bactericides, if necessary, only immediately before use (tank mix). These means can be added to the be mixed in a weight ratio of 1:10 to 10: 1.
  • compositions according to the invention can also be present together with other active compounds which, e.g. with herbicides, insecticides, growth regulators, fungicides or also with fertilizers. Mixing the compounds I or the compositions containing them in the use form as fungicides with other fungicides results in an enlargement of the fungicidal spectrum of action in many cases.
  • Sulfur, dithiocarbamates and their derivatives such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, manganese ethylene bisdithiocarbamate, manganese-zinc-ethylenediamine-bis-dithiocarbamate, tetramethylthi-ammonium-bis-dithiocarbamate, tetramethyl-ammonia-bis-dithiocarbamate, , Ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate), zinc (N, N'-propylene-bis-dithiocarbamate), N, N'-polypropylene-bis- (thiocarbamoyl) disulfide; Nitroderivate, such as dinitro- (1-methylheptyl) phenylcrotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-
  • Heterocyclic substances such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, O, O-diethyl-phthalimidophosphonothioate, 5-amino-1- [bis- (dimethylamino) phosphinyl] -3-phenyl-1, 2,4-triazole, 2,3-dicyano-1, 4-dithioanthraquinone, 2-thio-1, 3-dithiolo [4,5-b] quinoxaline, 1 - (Butylcarbamoyl) -2- benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benzimidazole, 2- (furyl- (2)) -benzimidazole, 2- (thiazolyl- (4)) - benzimidazoI, N- (1, 1, 2, 2-tetrachloroe
  • id, .N Formyl-N-morpholine-2,2,2-trichloroethyl acetal, piperazine-1,4-diylbis-1- (2,2,2-trichloroethyl) -formamide, 1- (3,4-dichloroanilino) -1-formylamino- 2,2,2-trichloroethane, 2,6-dimethyl-N-tridecyl-morpholine or its salts, 2,6-dimethyl-N-cyclododecyl-morpholine or its salts, N- [3- (p-tert. -Butylphenyl) -2-methylpropyl] -cis-2,6-dimethyl-morpholine, N- [3- (p-tert-butylphenyl) -
  • Strobilurins such as methyl-E-methoxyimino- [- (o-tolyloxy) -o-tolyl] acetate, methyl-E-2- ⁇ 2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl ⁇ -3-methoxyacrylate, methyl-E-methoxyimino- [- (2-phenoxyphenyl)] - acetamide, methyl-E-methoxyimino- [ ⁇ - (2,5-dimethylphenoxy) -o-tolyI] -acetamide, • anilinopyrimidines such as N - (4,6-Dimethylpyrimidin-2-yl) aniline, N- [4-methyl-6- (1-propynyl) pyrimidin-2-yl] aniline, N- [4-methyl-6-cyclopropyl- pyrimidin-2-yl] aniline,
  • Phenylpyrroles such as 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyrrole-3-carbonitrile,
  • Cinnamic acid amides such as 3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) acrylic morpholide, and various fungicides such as dodecylguanidine acetate,
  • Example 1 3-trifluoromethyl-picolinic acid (ortho-cyclohexyl) anilide:
  • the contents of the autoclave were poured into 1000 g of ice water, made alkaline with 40% strength by weight aqueous potassium hydroxide solution, washed 3 times with 350 ml of methylene chloride, the methylene chloride phase was separated off, washed once with 300 ml of water and then dried organic phase with magnesium sulfate. After distilling off the solvent in vacuo, a residue was obtained which was distilled in vacuo over a 15 cm Vigreux column. 61.9 g of the title compound were obtained as a fraction at 98-99 ° C. (10 mbar) with a GC purity of 88.7%.
  • Triethylamine dissolved. 0.72 g of 3-trifluoromethylpicolinoyl chloride was added and the mixture was stirred at room temperature for 14 h. The reaction mixture was then washed once each with aqueous sodium hydrogen carbonate and dilute hydrochloric acid and twice with water. The organic phase was dried over sodium sulfate and concentrated in vacuo. After chromatographic cleaning of the Residue on silica gel with a mixture of cyclohexane and methyl tert-butyl ether gives 740 mg of the target compound with a fixed point of 111-116 ° C.
  • the active ingredients were prepared as a stock solution with 0.25% by weight of active ingredient in acetone or dimethyl sulfoxide (DMSO). 1% by weight of the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) was added to this solution and diluted with water to the desired concentration.
  • DMSO dimethyl sulfoxide

Abstract

The invention relates to 3-trifluoromethyl picolinic acid anilides of general formula (I), wherein X represents oxygen, sulfur, or a direct bond, W represents oxygen or sulfur, n represents 0, 1, 2, 3, or 4, and the substituents have the meaning indicated in the claims, as well as the agriculturally useful salts of (I). The invention further relates to the use of said 3-trifluoromethyl picolinic acid anilides of general formula (I) and the agriculturally acceptable salts thereof as fungicides as well as plant protection agents containing the same.

Description

3-Trifluormethylpicolinsäureanilide und ihre Verwendung als Fungizide3-trifluoromethylpicolinic acid anilides and their use as fungicides
Beschreibungdescription
Die vorliegende Erfindung betrifft 3-Trifluormethylpicolinsäureanilide mit fungizider Wirksamkeit und ihre Verwendung als Fungizide, d.h. zur Bekämpfung von Schadpilzen.The present invention relates to 3-trifluoromethylpicolinic acid anilides with fungicidal activity and their use as fungicides, i.e. to combat harmful fungi.
Hetarylanilide mit fungizider Wirksamkeit sind Gegenstand zahlreicher Patentanmel- düngen (siehe beispielsweise WO 86/02641 , JP 01313402, US 4,877,441 , EP 371950, WO 93/11117, EP 545099, DE 4204766, DE 4204768, EP 591699, EP 589301 , JP 07145156, JP 08092223, WO 97/08148, WO 98/03500, EP 824099, EP 846416, WO 00/09482, WO 01/42223, EP 1110454, EP 1110956, WO 01/49664, JP 2001-302605, WO 02/08195, WO 02/08197, WO 02/38542, WO 02/59086, WO 02/064562, WO 03/010149, WO 03/66609, WO 03/66610, WO 03/69995, WO 03/74491 und WO 03/70705). Die dort beschriebenen Hetarylanilide können jedoch, insbesondere bei niedrigen Aufwandmengen, nicht in vollem Umfang zufrieden stellen.Hetarylanilides with fungicidal activity are the subject of numerous patent applications (see, for example, WO 86/02641, JP 01313402, US 4,877,441, EP 371950, WO 93/11117, EP 545099, DE 4204766, DE 4204768, EP 591699, EP 589301, JP 07145156, JP 08092223, WO 97/08148, WO 98/03500, EP 824099, EP 846416, WO 00/09482, WO 01/42223, EP 1110454, EP 1110956, WO 01/49664, JP 2001-302605, WO 02/08195, WO 02/08197, WO 02/38542, WO 02/59086, WO 02/064562, WO 03/010149, WO 03/66609, WO 03/66610, WO 03/69995, WO 03/74491 and WO 03/70705) , The hetarylanilides described there, however, cannot be completely satisfactory, especially when the application rates are low.
Aus JP 58096069 sind fungizid wirksame Picolinsäureanilide der allgemeinen FormelJP 58096069 describes fungicidally active picolinic anilides of the general formula
Figure imgf000003_0001
Figure imgf000003_0001
worin R für CH3 oder CF3 steht, bekannt. Die fungizide Wirksamkeit dieser Verbindungen ist jedoch nicht zufriedenstellend.where R is CH 3 or CF 3 , known. However, the fungicidal activity of these compounds is unsatisfactory.
Der vorliegenden Erfindung liegt daher die Aufgabe zugrunde weitere fungizid wirkende Verbindungen bereitzustellen, die die Nachteile der aus dem Stand der Technik bekannten Verbindungen überwinden und insbesondere eine verbesserte Wirkung bei niedrigen Aufwandmengen zeigen. Außerdem sollten diese Verbindungen eine gute Nutzpflanzenverträglichkeit aufweisen und möglichst keine oder nur eine geringe Schädlichkeit gegenüber tierischen Nutzungen zeigen.The present invention is therefore based on the object of providing further fungicidally active compounds which overcome the disadvantages of the compounds known from the prior art and in particular have an improved action at low application rates. In addition, these compounds should have good crop tolerance and should show little or no harm to animal use if possible.
Diese Aufgabe konnten gelöst werden durch die im Folgenden beschriebenen 3- Trifluormethylpicolinsäureanilide der allgemeinen Formel I und durch ihre landwirt- schaftlich verträglichen Salze. Die vorliegende Erfindung betrifft daher 3-TrifluormethyIpicolinsäureanilide der allgemeinen Formel I,This object could be achieved by the 3-trifluoromethylpicolinic anilides of the general formula I described below and by their agriculturally compatible salts. The present invention therefore relates to 3-trifluoromethylpicolinic acid anilides of the general formula I,
Figure imgf000004_0001
Figure imgf000004_0001
worin n für 0, 1 , 2, 3 oder 4 steht und die Substituenten die folgende Bedeutung haben:where n is 0, 1, 2, 3 or 4 and the substituents have the following meaning:
X O, S oder direkte Bindung; W O oder S;X O, S or direct bond; W O or S;
R1, R2, R3 unabhängig voneinander Wasserstoff, Halogen, Nitro, CN, C C4-Alkyl, C3- C6-Cycloalkyl, C2-C4-Alkenyl, C2-C4-Alkinyl, C C4-Alkoxy, wobei die Wasserstoffatome in den 4 zuletzt genannten Gruppen teilweise oder vollständig durch Halogen substituiert sein können; R4 Wasserstoff, OH, C C4-Alkyl, C3-C6-Cycloalkyl, Cι-C4-Alkox , wobei dieR 1 , R 2 , R 3 independently of one another are hydrogen, halogen, nitro, CN, CC 4 -alkyl, C 3 - C 6 -cycloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, CC 4 - Alkoxy, where the hydrogen atoms in the last 4 groups mentioned can be partially or completely substituted by halogen; R 4 is hydrogen, OH, CC 4 alkyl, C 3 -C 6 cycloalkyl, -C-C 4 alkox, the
Wasserstoffatome in den 3 zuletzt genannten Gruppen teilweise oder vollständig durch Halogen substituiert sein können; R5 unsubstituiertes C -C12-Alkyl, C3-C12-Cycloalkyl, C3-Cι2-Alkenyl, C5-C12-Hydrogen atoms in the last 3 groups mentioned can be partially or completely substituted by halogen; R 5 unsubstituted C -C 12 alkyl, C 3 -C 12 cycloalkyl, C 3 -Cι 2 alkenyl, C 5 -C 12 -
Cycloalkenyl, C3-C12-Alkinyl,
Figure imgf000004_0002
wobei die 5 letztgenannten Gruppen jeweils 1 , 2 oder 3 Substituenten R9 aufweisen können, und wobei die Wasserstoffatome in den 5 letztgenannten Gruppen teilweise oder vollständig durch Halogen substituiert sein können; Cι-Cι2-Halogenalkyl, C Cι2-Alkyl, das 1 , 2 oder 3 Substituenten R11 aufweist, eine Gruppe -C(R10)=NOR8, eine Gruppe -C(O)NR13R14;Cycloalkenyl, C 3 -C 12 alkynyl,
Figure imgf000004_0002
wherein the 5 latter groups can each have 1, 2 or 3 substituents R 9 , and wherein the hydrogen atoms in the 5 latter groups can be partially or completely substituted by halogen; Cι-Cι 2 -haloalkyl, C 2 Cι alkyl having 1, 2 or 3 substituents R 11, a group -C (R 10) = NOR 8, a group -C (O) NR 13 R 14;
Phenyl, Phenyl-C C6-alkyl, Phenyl-C2-C6-alkenyl, Phenyl-C2-C6-alkinyl, Phenyloxy-C Ce-alkyl, Phenyloxy-C2-C6-alkenyl, Phenyloxy-C^Ce-alkinyl, wobei der Alkyl-, Alkenyl- und der Alkinyl-Teil in den 6 zuletzt genannten Gruppen 1 , 2, 3 oder 4 Substituenten R11 aufweisen kann und der Phenyl- ring in den 7 zuletzt genannten Gruppen 1 , 2, 3 oder 4 Reste R7 tragen kann; R6 die für R1 genannten, von Wasserstoff verschiedenen Bedeutungen;Phenyl, phenyl-C 6 alkyl, phenyl C 2 -C 6 -alkenyl, phenyl C 2 -C 6 -alkynyl, phenyloxy-C Ce-alkyl, phenyloxy-C 2 -C 6 -alkenyl, phenyloxy-C ^ Ce-alkynyl, where the alkyl, alkenyl and alkynyl part in the 6 last-mentioned groups can have 1, 2, 3 or 4 substituents R 11 and the phenyl ring in the 7 last-mentioned groups 1, 2, Can carry 3 or 4 R 7 radicals; R 6 has the meanings given for R 1 and different from hydrogen;
R7 C C4-Alkyl, C3-C6- Cycloalkyl, C C^AIkoxy, C2-C4-Alkenyl, C2-C4-R 7 CC 4 alkyl, C 3 -C 6 cycloalkyl, CC ^ alkoxy, C 2 -C 4 alkenyl, C 2 -C 4 -
Alkenyloxy, C2-C4-Alkinyl, C2-C4-Alkinyloxy, wobei die Wasserstoffatome in diesen 7 Gruppen teilweise oder vollständig durch Halogen substituiert sein können, OH, Halogen, Nitro, CN, C C4-Alkylthio, CrC4-Alkylsulfonyl, - C(O)R12, NR13R14, -C(O)NR13R14, -C(S)NR13R14, -C(R10)=NOR8, Phenyl, das 1 , 2, 3 oder 4 der unter R6 genannten Gruppen aufweisen kann, Phenoxy, das 1 , 2, 3 oder 4 der unter R6 genannten Gruppen aufweisen kann, C C6- Alkyl-Phenyl, wobei die Wasserstoffatome des Alkylteils teilweise oder vollständig durch Halogen substituiert sein können und der Phenylring 1 , 2, 3 oder 4 der unter R6 genannten Gruppen aufweisen kann, wobei zwei an benachbarte Kohlenstoffatome gebundene Reste R7 auch für CH=CH-CH=CH oder eine Alkylenkette mit 3 bis 5 Gliedern stehen können, worin 1 oder 2 nicht benachbarte CH2-Gruppen auch durch Sauerstoff oderAlkenyloxy, C 2 -C 4 alkynyl, C 2 -C 4 alkynyloxy, the hydrogen atoms in these 7 groups being partially or completely substituted by halogen can, OH, halogen, nitro, CN, CC 4 -alkylthio, C r C 4 -alkylsulfonyl, - C (O) R 12 , NR 13 R 14 , -C (O) NR 13 R 14 , -C (S) NR 13 R 14 , -C (R 10 ) = NOR 8 , phenyl, which may have 1, 2, 3 or 4 of the groups mentioned under R 6 , phenoxy, the 1, 2, 3 or 4 of the groups mentioned under R 6 can have CC 6 - alkyl-phenyl, where the hydrogen atoms of the alkyl part can be partially or completely substituted by halogen and the phenyl ring can have 1, 2, 3 or 4 of the groups mentioned under R 6 , where two radicals R. bonded to adjacent carbon atoms 7 can also stand for CH = CH-CH = CH or an alkylene chain with 3 to 5 links, in which 1 or 2 non-adjacent CH 2 groups can also be formed by oxygen or
Schwefel ersetzt sein können und worin ein Teil oder alle Wasserstoffe durch Halogen ersetzt sein können; R8 Cι-C4-Alkyl, C3-C6-Cycloalkyl, C2-C -Alkenyl, C2-C4-Alkinyl, wobei die Wasserstoffatome in diesen 4 Gruppen teilweise oder vollständig durch Halogen substituiert sein können,Sulfur can be replaced and in which some or all of the hydrogen can be replaced by halogen; R 8 -C 4 alkyl, C 3 -C 6 cycloalkyl, C 2 -C alkenyl, C 2 -C 4 alkynyl, where the hydrogen atoms in these 4 groups can be partially or completely substituted by halogen,
Phenyl oder Phenyl-C C6-alkyl, wobei Phenyl in den zwei letztgenannten Resten 1 , 2, 3 oder 4 der unter R6 genannten Gruppen aufweisen kann; R9 C GrAlkyl, C C8-Alkoxy, C2-C8-Alkenyloxy, C2-C8-Alkinyloxy, C C4-Phenyl or phenyl-C 6 alkyl, where phenyl in the latter two radicals can have 1, 2, 3 or 4 of the groups mentioned under R 6 ; R 9 C GrAlkyl, CC 8 alkoxy, C 2 -C 8 alkenyloxy, C 2 -C 8 alkynyloxy, CC 4 -
Alkoxy-CrCs-alkoxy, wobei die Wasserstoffatome in diesen Gruppen teil- weise oder vollständig durch Halogen substituiert sein können;Alkoxy-CrCs-alkoxy, where the hydrogen atoms in these groups can be partially or completely substituted by halogen;
R10 Wasserstoff, Halogen, Cι-C8-Alkoxy, C2-C8-Alkenyloxy, C2-C8-Alkinyloxy,R 10 is hydrogen, halogen, -CC 8 alkoxy, C 2 -C 8 alkenyloxy, C 2 -C 8 alkynyloxy,
Cι-C4-Alkoxy-C C8-aIkoxy, CrC12-Alkyl, C3-C12-Cycloalkyl, C2-C12-Alkenyl, C5-C12-Cycloalkenyl, Cs-C^-Cycloalkyl-CrC^alkyl, wobei die Wasserstoffatome in den 9 zuletzt genannten Gruppen teilweise oder vollständig durch Halogen substituiert sein können;-C-C 4 alkoxy-C C 8 -alkoxy, C r C 12 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 12 alkenyl, C 5 -C 12 cycloalkenyl, Cs-C ^ cycloalkyl -CrC ^ alkyl, where the hydrogen atoms in the 9 last-mentioned groups can be partially or completely substituted by halogen;
Phenyl, das 1 , 2, 3 oder 4 der unter R7 genannten Gruppen aufweisen kann, R11 C C4-Alkyl, C C8-Alkoxy, d-Cs-Alkoxy-C Cs-alkoxy, C2-C8-Alkenyloxy,Phenyl which can have 1, 2, 3 or 4 of the groups mentioned under R 7 , R 11 CC 4 alkyl, CC 8 alkoxy, d-Cs-alkoxy-C Cs-alkoxy, C 2 -C 8 -alkenoxy,
C2-C8-Alkinyloxy, CrC^AIkoxy-C^Cs-alkoxy, wobei die Wasserstoffatome in diesen Gruppen teilweise oder vollständig durch Halogen substituiert sein können, oder Halogen; R12 Wasserstoff, OH, C C -Alkyl, C C4-Alkoxy, C2-C4-Alkenyl, C2-C4-Alkinyl,C 2 -C 8 alkynyloxy, CrC ^ alkoxy-C ^ Cs-alkoxy, where the hydrogen atoms in these groups can be partially or completely substituted by halogen, or halogen; R 12 is hydrogen, OH, CC alkyl, CC 4 alkoxy, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl,
C2-C4-Alkenyloxy, C2-C4-Alkinyloxy, Crd-Alkoxy-Crd-alkoxy, wobei die Wasserstoffatome in den 7 zuletzt genannten Gruppen teilweise oder voll- ständig durch Halogen substituiert sein können;C 2 -C 4 alkenyloxy, C 2 -C 4 alkynyloxy, Crd-alkoxy-Crd-alkoxy, where the hydrogen atoms in the 7 last-mentioned groups can be partially or completely substituted by halogen;
R13, R14 unabhängig voneinander Wasserstoff, C C4-Alkyl, C2-C -Älkenyl, C2-C4- Alkinyl, wobei die Wasserstoffatome in diesen Gruppen teilweise oder vollständig durch Halogen substituiert sein können;R 13 , R 14 independently of one another are hydrogen, CC 4 -alkyl, C 2 -C -alkenyl, C 2 -C 4 -alkynyl, where the hydrogen atoms in these groups can be partially or completely substituted by halogen;
und die landwirtschaftlich brauchbaren Salze von I. Die vorliegende Erfindung betrifft außerdem die Verwendung der 3-Trifluormethyl- picolinsäureanilide der allgemeinen Formel I und deren landwirtschaftlich verträglich Salze als Fungizide sowie diese enthaltende Pflanzenschutzmittel.and the agriculturally useful salts of I. The present invention also relates to the use of the 3-trifluoromethylpicolinic acid anilides of the general formula I and their agriculturally acceptable salts as fungicides, and to crop protection agents containing them.
Die vorliegende Erfindung betrifft weiterhin ein Verfahren zur Bekämpfung von pflan- zenpathogenen Pilzen (Schadpilzen), das dadurch gekennzeichnet ist, dass man die Schadpilze, deren Lebensraum oder die von ihnen freizuhaltenden Pflanzen, Flächen, Materialien oder Räume mit einer fungizid wirksamen Menge eines 3- Trifluormethylpicolinsäureanilids der allgemeinen Formel I und/oder einem landwirtschaftlich verträglichen Salz von I behandelt.The present invention further relates to a method for combating phytopathogenic fungi (harmful fungi), which is characterized in that the harmful fungi, their habitat or the plants, areas, materials or spaces to be kept free by them with a fungicidally effective amount of a 3- Trifluoromethylpicolinsäureanilids of general formula I and / or an agriculturally acceptable salt of I treated.
Die 3-Trifluormethylpicolinsäureanilide der Formel I können je nach Art der Substituenten ein oder mehrere Chiralitätszentren aufweisen und liegen dann als Enantiomeren- oder Diastereomerengemische vor. Gegenstand der Erfindung sind sowohl die reinen Enantiomere oder Diastereomere als auch deren Gemische. Geeignete Verbindungen der Formel I umfassen auch alle möglichen Stereoisomere (cis/trans-lsomere) und Gemische davon.Depending on the nature of the substituents, the 3-trifluoromethylpicolinic acid anilides of the formula I can have one or more centers of chirality and are then present as mixtures of enantiomers or diastereomers. The invention relates both to the pure enantiomers or diastereomers and to their mixtures. Suitable compounds of formula I also include all possible stereoisomers (cis / trans isomers) and mixtures thereof.
Unter landwirtschaftlich brauchbaren Salzen kommen vor allem die Salze derjenigen Kationen oder die Säureadditionssalze derjenigen Säuren in Betracht, deren Kationen beziehungsweise Anionen die fungizide Wirkung der Verbindungen I nicht negativ beeinträchtigen. So kommen als Kationen insbesondere die Ionen der Alkalimetalle, vorzugsweise Natrium und Kalium, der Erdalkalimetalle, vorzugsweise Calcium, Magnesi- um und Barium, und der Übergangsmetalle, vorzugsweise Mangan, Kupfer, Zink und Eisen, sowie das Ammoniumion, das gewünschtenfalls ein bis vier C C4-Alkylsubsti- tuenten und/oder einen Phenyl- oder Benzylsubstituenten tragen kann, vorzugsweise Diisopropylammonium, Tetramethylammonium, Tetrabutylammonium, Trimethylbenzyl- ammonium, des weiteren Phosphoniumionen, Sulfoniumionen, vorzugsweise Tri(C C -alkyl)sulfonium und Sulfoxoniumionen, vorzugsweise Tri(Cι-C4-alkyl)sulf- oxonium, in Betracht.Agriculturally useful salts include, in particular, the salts of those cations or the acid addition salts of those acids whose cations or anions do not adversely affect the fungicidal activity of the compounds I. So come as cations in particular the ions of the alkali metals, preferably sodium and potassium, the alkaline earth metals, preferably calcium, magnesium and barium, and the transition metals, preferably manganese, copper, zinc and iron, and the ammonium ion, if desired one to four CC 4 alkyl substituents and / or can carry a phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri (CC-alkyl) sulfonium and sulfoxonium ions C, preferably tri (Cι-Cι 4- alkyl) sulfoxonium, into consideration.
Anionen von brauchbaren Säureadditionssalzen sind in erster Linie Chlorid, Bromid, Fluorid, Hydrogensulfat, Sulfat, Dihydrogenphosphat, Hydrogenphosphat, Phosphat, Nitrat, Hydrogencarbonat, Carbonat, Hexafluorosilikat, Hexafluorophosphat, Benzoat, sowie die Anionen von CrC4-AIkansäuren, vorzugsweise Formiat, Acetat, Propionat und Butyrat. Sie können durch Reaktion von I mit einer Säure des entsprechenden Anions, vorzugsweise der Chlorwasserstoffsäure, Bromwasserstoffsäure, Schwefelsäure, Phosphorsäure oder Salpetersäure, gebildet werden. Bei den in den vorstehenden Formeln angegebenen Definitionen der Variablen werden Sammelbegriffe verwendet, die allgemein repräsentativ für die jeweiligen Substituenten stehen. Die Bedeutung Cn-Cm gibt die jeweils mögliche Anzahl von Kohlenstoffatomen in dem jeweiligen Substituenten oder Substituententeil an. Sämtliche Kohlenstoffketten, also alle Alkyl-, Halogenalkyl-, Phenylalkyl-, Alkenyl-, Halogenalkenyl-, Phenylalkenyl-, Alkinyl-, Halogenalkinyl- und Phenylalkinyl-Teile können geradkettig oder verzweigt sein. Halogenierte Substituenten tragen vorzugsweise ein bis fünf gleiche oder verschiedene Halogenatome. Die Bedeutung Halogen steht jeweils für Fluor, Chlor, Brom oder lod.Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, as well as the anions of CrC 4 -alkanoic acids, preferably formic acids, preferably formic acids, preferably Propionate and butyrate. They can be formed by reacting I with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid. In the definitions of the variables given in the formulas above, collective terms are used which are generally representative of the respective substituents. The meaning C n -C m indicates the possible number of carbon atoms in the respective substituent or part of the substituent. All carbon chains, that is, all alkyl, haloalkyl, phenylalkyl, alkenyl, haloalkenyl, phenylalkenyl, alkynyl, haloalkynyl and phenylalkynyl parts can be straight-chain or branched. Halogenated substituents preferably carry one to five identical or different halogen atoms. Halogen is fluorine, chlorine, bromine or iodine.
Ferner stehen beispielsweise:Furthermore, for example:
C C -Alkyl sowie die Alkylteile in Alkoxyalkyl, Alkylsulfonyl und Alkylthio für: CH3, C2H5, CH2-C2H5, CH(CH3)2> n-Butyl, CH(CH3)-C2H5, CH -CH(CH3)2 oder C(CH3)3;CC alkyl and the alkyl parts in alkoxyalkyl, alkylsulfonyl and alkylthio for: CH 3 , C 2 H 5 , CH 2 -C 2 H 5 , CH (CH 3 ) 2> n-butyl, CH (CH 3 ) -C 2 H 5 , CH -CH (CH 3 ) 2 or C (CH 3 ) 3 ;
C C4-Halogenalkyl: für einen CrC^Alkylrest wie vorstehend genannt, worin die Wasserstoffatome teilweise, z.B. 1, 2 oder 3, oder vollständig durch Halogen wie Fluor, Chlor, Brom und/oder lod, insbesondere durch Chlor und/oder Fluor und speziell durch Fluor substituiert sind, also z.B. CH2F, CHF2, CF3, CH2CI, CH(CI)2,CC 4 haloalkyl: for a CrC ^ alkyl radical as mentioned above, in which the hydrogen atoms are partially, for example 1, 2 or 3, or completely by halogen such as fluorine, chlorine, bromine and / or iodine, in particular by chlorine and / or fluorine and especially are substituted by fluorine, for example CH 2 F, CHF 2 , CF 3 , CH 2 CI, CH (CI) 2 ,
C(CI)3, Chlorfluormethyl, Dichlorfluormethyl, Chlordifluormethyl, 2-Fluorethyϊ 2-Chlorethyl, 2-Bromethyl, 2-lodethyl, 2,2-Difluorethyl, 2,2,2-Trifluorethyl, 2-Chlor-2-fluorethyl, 2-Chlor-2,2-difluorethyl, 2,2-Dichlor-2-fluorethyl, 2,2,2-Trichlorethyl, C2F5, 2-Fluorpropyi, 3-FluorpropyI, 2,2-Difluorpropyl, 2,3-Difluorpropyl, 2-Chlorpropyl, 3-Chlorpropyl, 2,3-Dichlorpropyl, 2-Brompropyl,C (CI) 3 , chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2nd -Chlor-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, C 2 F 5 , 2-fluoropropyi, 3-fluoropropyI, 2,2-difluoropropyl, 2,3- Difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl,
3-Brompropyl, 3,3,3-Trifluorpropyl, 3,3,3-Trichlorpropyl, CHz-C2F5, CF2-C2F5, 1 -(Fluormethyl)-2-fluorethyl, 1 -(Chlormethyl)-2-chlorethyl, 1-(Brommethyl)-2-bromethyl, 4-Fluorbutyl, 4-Chlorbutyl, 4-Brombutyl oder Nona- fluorbutyl;3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, CHz-C 2 F 5 , CF 2 -C 2 F 5 , 1 - (fluoromethyl) -2-fluoroethyl, 1 - (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromomethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or non-fluorobutyl;
C C12-Alkyl: für einen gesättigten Kohlenwasserstoffrest mit 1 bis 12 C-Atomen, z.B. für einen CrC^Alkylrest wie vorstehend genannt, oder für z.B. n-Pentyl, 1-Methylbutyl, 2-Methylbutyl, 3-Methylbutyl, 2,2-Dimethylpropyl, 1-Ethylpropyl, n-Hexyl, 1 ,1-Dimethylpropyl, 1 ,2-Dimethylpropyl, 1-Methylpentyl, 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1 ,1-Dimethylbutyl, 1 ,2-Dimethylbutyl,CC 12 alkyl: for a saturated hydrocarbon radical having 1 to 12 carbon atoms, for example for a CrC ^ alkyl radical as mentioned above, or for for example n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2- Dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl,
1 ,3-Dimethylbutyl, 2,2-Dimethylbutyl, 2,3-Dimethylbutyl, 3,3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbutyl, 1 ,1 ,2-Trimethylpropyl, 1 ,2,2-Trimethylpropyl, 1-Ethyl-1-methylpropyl oder 1-Ethyl-2-methyIpropyl, vorzugsweise für CH3, C2H5, CH2-C2H5, CH(CH3)2, n-Butyl, C(CH3)3, n-Pentyl, n-Hexyl, n-Heptyl oder n-Octyl; C Cι2-Halogenalkyl: für einen C C12-Alkylrest wie vorstehend genannt, worin die Wasserstoffatome teilweise, z.B. 1 , 2 oder 3, oder vollständig durch Halogen, insbesondere durch Chlor und/oder Fluor und speziell durch Fluor substituiert sind, also z.B. für einen der unter C C4-Halogenalkyl genannten Reste oder für 5-Fluor-1-pentyl, 5-Chlor-1-pentyl, 5-Brom-1-pentyl, 5-lod-1-pentyl,1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1- Ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl, preferably for CH 3 , C 2 H 5 , CH 2 -C 2 H 5 , CH (CH 3 ) 2 , n-butyl, C (CH 3 ) 3 , n-pentyl, n-hexyl, n-heptyl or n-octyl; C -C 2 haloalkyl: for a CC 12 alkyl radical as mentioned above, wherein the hydrogen atoms are partially, for example 1, 2 or 3, or completely substituted by halogen, in particular by chlorine and / or fluorine and especially by fluorine, for example for one of the radicals mentioned under CC 4 -haloalkyl or for 5-fluoro-1-pentyl, 5-chloro-1-pentyl, 5-bromo-1-pentyl, 5-iodo-1-pentyl,
5,5,5-Trichlor-1-pentyl, Undecafluorpentyl, 6-Fluor-1-hexyl, 6-Chlor-1-hexyl, 6-Brom-1-hexyl, 6-lod-1-hexyl, 6,6,6-Trichlor-1-hexyl oder Tridecafluorhexyl;5,5,5-trichloro-1-pentyl, undecafluoropentyl, 6-fluoro-1-hexyl, 6-chloro-1-hexyl, 6-bromo-1-hexyl, 6-iodo-1-hexyl, 6.6, 6-trichloro-1-hexyl or tridecafluorohexyl;
C2-C4-Alkenyl sowie die Alkenylteile in Alkenyloxy: ungesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit 2 bis 4 Kohlenstoffatomen und einerC 2 -C 4 alkenyl and the alkenyl parts in alkenyloxy: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4 carbon atoms and one
Doppelbindung in einer beliebigen Position, z.B. Ethenyl, 1-Propenyl, 2-Propenyl, 1-Methylethenyl, 1-Buten-1-yl, 1-Buten-2-yl, 1-Buten-3-yl, 2-Buten-1-yl, 1 -Methyl-prop-1 -en-1 -yl, 2-Methyl-prop-1 -en-1 -yl, 1 -Methyl-prop-2-en-1 -yl, 2-Methyl-prop-2-en-1-yl;Double bond in any position, e.g. Ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-buten-1-yl, 1-buten-2-yl, 1-buten-3-yl, 2-buten-1-yl, 1-methyl prop-1 -en-1 -yl, 2-methyl-prop-1 -en-1 -yl, 1-methyl-prop-2-en-1 -yl, 2-methyl-prop-2-en-1- yl;
C2-Cι2-Alkenyl: ungesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit 2 bis 12 Kohlenstoffatomen und einer Doppelbindung in einer beliebigen Position, z.B. für C2-C4-Alkenyl wie vorstehend genannt sowie z. B. für: n-Penten-1-yl, n-Penten-2-yl, n-Penten-3-yl, n-Penten-4-yl, 1-Methyl-but-1-en-1-yl, 2-Methyl-but-1-en-1-yl, 3-Methyl-but-1-en-1-yI,C 2 -C 2 alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 12 carbon atoms and a double bond in any position, for example for C 2 -C 4 alkenyl as mentioned above and z. B. for: n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, 1-methyl-but-1-en-1-yl, 2-methyl-but-1-en-1-yl, 3-methyl-but-1-en-1-yl,
1-Methyl-but-2-en-1-yl, 2-Methyl-but-2-en-1-yl, 3-Methyl-but-2-en-1-yl, 1-Methyl-but-3-en-1-yl, 2-Methyl-but-3-en-1-yl, 3-Methyl-but-3-en-1-yl, 1 ,1-Dimethyl-prop-2-en-1-yl, 1 ,2-Dimethyl-prop-1-en-1-yl, 1 ,2-Dimethyl-prop-2-en-1-yl, 1-EthyI-prop-1-en-2-yl, 1-Ethyl-prop-2-en-1-yl, n-Hex-1-en-1-yl, n-Hex-2-en-1-yl, n-Hex-3-en-1-yl, n-Hex-4-en-1-yl, n-Hex-5-en-1 -yl, 1 -Methyl-pent-1 -en-1 -yl, 2-Methyl-pent-1-en-1 -yl, 3-Methyl-pent-1 -en-1 -yl, 4-Methyl-pent-1 -en-1 -yl, 1 -Methyl-pent-2-en-1 -yl, 2-Methyl-pent-2-en-1 -yl, 3-Methyl-pent-2-en-1 -yl, 4-Methyl-pent-2-en-1 -yl, 1-Methyl-pent-3-en-1-yl, 2-Methyl-pent-3-en-1-yl, 3-Methyl-pent-3-en-1-yl, 4-Methyl-pent-3-en-1-yl, 1-Methyl-pent-4-en-1-yl, 2-Methyl-pent-4-en-1-yl,1-methyl-but-2-en-1-yl, 2-methyl-but-2-en-1-yl, 3-methyl-but-2-en-1-yl, 1-methyl-but-3- en-1-yl, 2-methyl-but-3-en-1-yl, 3-methyl-but-3-en-1-yl, 1, 1-dimethyl-prop-2-en-1-yl, 1, 2-Dimethyl-prop-1-en-1-yl, 1, 2-dimethyl-prop-2-en-1-yl, 1-ethyl-prop-1-en-2-yl, 1-ethyl prop-2-en-1-yl, n-hex-1-en-1-yl, n-hex-2-en-1-yl, n-hex-3-en-1-yl, n-hex 4-en-1-yl, n-hex-5-en-1-yl, 1-methyl-pent-1-en-1-yl, 2-methyl-pent-1-en-1-yl, 3- Methyl-pent-1-en-1-yl, 4-methyl-pent-1-en-1-yl, 1-methyl-pent-2-en-1-yl, 2-methyl-pent-2-en- 1 -yl, 3-methyl-pent-2-en-1-yl, 4-methyl-pent-2-en-1-yl, 1-methyl-pent-3-en-1-yl, 2-methyl pent-3-en-1-yl, 3-methyl-pent-3-en-1-yl, 4-methyl-pent-3-en-1-yl, 1-methyl-pent-4-en-1- yl, 2-methyl-pent-4-en-1-yl,
3-Methyl-pent-4-en-1 -yl, 4-Methyl-pent-4-en-1 -yl, 1 , 1 -Dimethyl-but-2-en-1 -yl , 1 ,1-Dimethyl-but-3-en-1-yl, 1 ,2-Dimethyl-but-1-en-1-yl, 1 ,2-Dimethyl-but-2-en-1-yl, 1 ,2-Dimethyl-but-3-en-1-yl, 1 ,3-Dimethyl-but-1 -en-1 -yl, 1 ,3-Dimethyl-but-2-en-1-yl, 1,3-Dimethyl-but-3-en-1-yl, 2,2-Dimethyl-but-3-en-1-yl,3-methyl-pent-4-en-1-yl, 4-methyl-pent-4-en-1-yl, 1, 1-dimethyl-but-2-en-1-yl, 1, 1-dimethyl but-3-en-1-yl, 1, 2-dimethyl-but-1-en-1-yl, 1, 2-dimethyl-but-2-en-1-yl, 1, 2-dimethyl-but- 3-en-1-yl, 1,3-dimethyl-but-1-en-1-yl, 1,3-dimethyl-but-2-en-1-yl, 1,3-dimethyl-but-3- en-1-yl, 2,2-dimethyl-but-3-en-1-yl,
2,3-Dimethyl-but-1-en-1-yl, 2,3-Dimethyl-but-2-en-1-yl, 2,3-Dimethyl-but-3-en-1-yl, 3,3-Dimethyl-but-1-en-1-yl, 3,3-Dimethyl-but-2-en-1-yl, 1 -Ethyl-but-1 -en-1 -yl, 1-Ethyl-but-2-en-1-yl, 1 -Ethyl-but-3-en-1 -yl, 2-Ethyl-but-1 -en-1 -yl, 2-Ethyl-but-2-en-1-yl, 2-Ethyl-but-3-en-1 -yl, 1 , 1 ,2-Trimethyl-prop-2-en-1 -yl, 1 -Ethyl-1 -methyl-prop-2-en-1 -yl, 1 -Ethyl-2-methyl-prop-1 -en-1 -yl oder 1 -Ethyl-2-methyl-prop-2-en-1 -yl;2,3-dimethyl-but-1-en-1-yl, 2,3-dimethyl-but-2-en-1-yl, 2,3-dimethyl-but-3-en-1-yl, 3, 3-dimethyl-but-1-en-1-yl, 3,3-dimethyl-but-2-en-1-yl, 1-ethyl-but-1-en-1-yl, 1-ethyl-but- 2-en-1-yl, 1-ethyl-but-3-en-1-yl, 2-ethyl-but-1-en-1-yl, 2-ethyl-but-2-en-1-yl, 2-ethyl-but-3-en-1-yl, 1, 1, 2-trimethyl-prop-2-en-1-yl, 1-ethyl-1-methyl-prop-2-en-1 -yl, 1-ethyl-2-methyl-prop-1-en-1 -yl or 1-ethyl-2-methyl-prop-2-en- 1 -yl;
C2-C4-Alkinyl sowie die Alkinylteile in Alkinyloxy: geradkettige oder verzweigte Kohlenwasserstoffgruppen mit 2 bis 4 Kohlenstoffatomen und einer Dreifachbindung in einer beliebigen Position, z.B. Ethinyl, 1-Propinyl, 2-Propinyl (=Propargyl), 1-Butinyl, 2-Butinyl, 3-Butinyl und 1-Methyl-2-propinyl;C 2 -C 4 alkynyl and the alkynyl parts in alkynyloxy: straight-chain or branched hydrocarbon groups with 2 to 4 carbon atoms and a triple bond in any position, for example ethynyl, 1-propynyl, 2-propynyl (= propargyl), 1-butynyl, 2 -Butinyl, 3-butynyl and 1-methyl-2-propynyl;
C2-Cι2-Alkinyl: für geradkettige oder verzweigte Kohlenwasserstoffgruppen mit 2 bis 12 Kohlenstoffatomen und einer Dreifachbindung in einer beliebigen Position, z.B. Ethinyl, Prop-1-in-1-yl, Prop-2-in-1-yl, n-But-1-in-1-yl, n-But-1-in-3-yl, n-But-1-in-4-yI, n-But-2-in-1-yl, n-Pent-1-in-1-yl, n-Pent-1-in-3-yl, n-Pent-1-in-4-yl, n-Pent-1-in-5-yl, n-Pent-2-in-1-yl, n-Pent-2-in-4-yI, n-Pent-2-in-5-yl, 3-Methyl-but-1-in-3-yl, 3-Methyl-but-1-in-4-yl, n-Hex-1-in-1-yl, n-Hex-1-in-3-yl, n-Hex-1-in-4-yl, n-Hex-1-in-5-yl, n-Hex-1-in-6-yl, n-Hex-2-in-1-yl, n-Hex-2-in-4-yl, n-Hex-2-in-5-yl, n-Hex-2-in-6-yl, n-Hex-3-in-1-yl, n-Hex-3-in-2-yl, 3-Methyl-pent-1-in-1-yl, 3-Methyl-pent-1-in-3-yl, 3-Methyl-pent-1-in-4-yl, 3-Methyl-pent-1-in-5-yl, 4-Methyl-pent-1-in-1-yl, 4-Methyl-pent-2-in-4-yl und 4-Methyl-pent-2-in-5-yl;C 2 -C 2 alkynyl: for straight-chain or branched hydrocarbon groups having 2 to 12 carbon atoms and a triple bond in any position, for example ethynyl, prop-1-in-1-yl, prop-2-in-1-yl, n -But-1-in-1-yl, n-but-1-in-3-yl, n-but-1-in-4-yl, n-but-2-in-1-yl, n-pent -1-in-1-yl, n-pent-1-in-3-yl, n-pent-1-in-4-yl, n-pent-1-in-5-yl, n-pent-2 -in-1-yl, n-pent-2-yn-4-yI, n-pent-2-yn-5-yl, 3-methyl-but-1-yn-3-yl, 3-methyl-but -1-in-4-yl, n-hex-1-in-1-yl, n-hex-1-in-3-yl, n-hex-1-in-4-yl, n-hex-1 -in-5-yl, n-hex-1-in-6-yl, n-hex-2-in-1-yl, n-hex-2-in-4-yl, n-hex-2-in -5-yl, n-Hex-2-in-6-yl, n-Hex-3-in-1-yl, n-Hex-3-in-2-yl, 3-methyl-pent-1-in -1-yl, 3-methyl-pent-1-in-3-yl, 3-methyl-pent-1-in-4-yl, 3-methyl-pent-1-in-5-yl, 4-methyl -pent-1-in-1-yl, 4-methyl-pent-2-in-4-yl and 4-methyl-pent-2-in-5-yl;
C C4-Alkoxy: für OCH3, OC2H5, OCH2-C2H5, OCH(CH3)2, n-Butoxy, OCH(CH3)-C2H5, OCH2-CH(CH3)2 oder OC(CH3)3;CC 4 alkoxy: for OCH 3 , OC 2 H 5 , OCH 2 -C 2 H 5 , OCH (CH 3 ) 2 , n-butoxy, OCH (CH 3 ) -C 2 H 5 , OCH 2 -CH (CH 3 ) 2 or OC (CH 3 ) 3 ;
C C4-Halogenalkoxy: für einen CrC4-Alkoxyrest wie vorstehend genannt, worin ein Teil, z.B. 1 , 2 oder 3 oder alle Wasserstoffatome durch. Halogen, insbesondere durch Chlor und/oder Fluor und speziell durch Fluor substituiert sind, also z.B. OCH2F, OCHF2l OCF3, OCH2CI, OCH(CI)2, OC(CI)3) Chlorfluormethoxy, Dich- lorfluormethoxy, Chlordifluormethoxy, 2-Fluorethoxy, 2-Chlorethoxy, 2-Bromethoxy, 2-lodethoxy, 2,2-Difluorethoxy, 2,2,2-Trifluorethoxy, 2-Chlor-2-fluorethoxy, 2-Chlor-2,2-difluorethoxy, 2,2-Dichlor-2-fluorethoxy,CC 4 haloalkoxy: for a CrC 4 alkoxy radical as mentioned above, in which a part, for example 1, 2 or 3 or all, of hydrogen atoms. Halogen, in particular substituted by chlorine and / or fluorine and especially by fluorine, for example OCH 2 F, OCHF 2l OCF 3 , OCH2CI, OCH (CI) 2 , OC (CI) 3) chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2 -Fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2.2 dichloro-2-fluoroethoxy,
2,2,2-Trichlorethoxy, OC2F5, 2-Fluorpropoxy, 3-Fluorpropoxy, 2,2-Difluorpropoxy, 2,3-Difluorpropoxy, 2-Chlorpropoxy, 3-Chlorpropoxy, 2,3-Dichlorpropoxy, - 2-Brompropoxy, 3-Brompropoxy, 3,3,3-Trifluorpropoxy, 3,3,3-Trichlorpropoxy, OCH2-C2F5, OCF2-C2F5) 1-(CH2F)-2-fluorethoxy, 1-(CH2CI)-2-chlorethoxy, 1-(CH2Br)-2-bromethoxy, 4-Fluorbutoxy, 4-Chlorbutoxy, 4-Brombutoxy o- der Nonafluorbutoxy, vorzugsweise für OCHF2, OCF3, Dichlorfluormethoxy, Chlordifluormethoxy oder 2,2,2-Trifluorethoxy;2,2,2-trichloroethoxy, OC 2 F 5 , 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, - 2- Bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH 2 -C 2 F 5 , OCF 2 -C 2 F 5) 1- (CH 2 F) -2-fluoroethoxy, 1- (CH 2 CI) -2-chloroethoxy, 1- (CH 2 Br) -2-bromethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy, preferably for OCHF 2 , OCF 3 , dichlorofluoromethoxy, Chlorodifluoromethoxy or 2,2,2-trifluoroethoxy;
C3-C6-Cycloalkyl: für Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl; C3-Ci2-Cycloalkyl: für einen mono-, bi- oder tricylischen Kohlenwasserstoffrest, z.B. für einen C3-C6-Cycloalkylrest wie vorstehend genannt oder für Cycloheptyl, Cyclooctyl, Bicyclo[2.2.1]heptyl, Bicyclo[2.2.2]octyl, Bicyclo[3.2.1]octyl, Bicyc- lo[3.3.0]octyl, Bicyclo[4.3.0]nonyl, Bicyclo[4.4.0]decyl oder Adamantyl;C 3 -C 6 cycloalkyl: for cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl; C 3 -Ci 2 -cycloalkyl: for a mono-, bi- or tricyclic hydrocarbon radical, for example for a C 3 -C 6 -cycloalkyl radical as mentioned above or for cycloheptyl, cyclooctyl, bicyclo [2.2.1] heptyl, bicyclo [2.2. 2] octyl, bicyclo [3.2.1] octyl, bicyclo [3.3.0] octyl, bicyclo [4.3.0] nonyl, bicyclo [4.4.0] decyl or adamantyl;
- C3-C12-Cycloalkyl-Cι-C4-alkyl: für C1-C4-Alkyl, welches mit C3-C12-CycloaIkyl substituiert ist, z.B. Cyclopropylmethyl, Cyclobutylmethyl, Cyclopentylmethyl, Cyclohexylmethyl, Cycloheptylmethyl, Cyclooctyl methyl, 2-(Cyclopropyl)ethyl, 2-(Cyclobutyl)ethyl, 2-(Cyclopentyl)ethyl, 2-(Cyclohexyl)ethyl, 2-(Cycloheptyl)ethyl, 2-(Cyclooctyl)ethyl, 3-(CycIopropyl)propyl,- C 3 -C 12 Cycloalkyl-C 4 -C 4 alkyl: for C 1 -C 4 alkyl which is substituted by C 3 -C 12 cycloalkyl, for example cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctyl methyl , 2- (cyclopropyl) ethyl, 2- (cyclobutyl) ethyl, 2- (cyclopentyl) ethyl, 2- (cyclohexyl) ethyl, 2- (cycloheptyl) ethyl, 2- (cyclooctyl) ethyl, 3- (cyclopropyl) propyl,
3-(Cyclobutyl)propyl, 3-(Cyclopentyl)propyl, 3-(CyclohexyI)propyl, 3-(Cycloheptyl)propyI, 3-(Cyclooctyl)propyl, 4-(Cyclopropyl)butyl, 4-(Cyclobutyl)butyl, 4-(Cyclopentyl)butyl, 4-(Cyclohexyl)butyl, 4-(Cycloheptyl)butyl, 4-(Cyclooctyl)butyl;3- (Cyclobutyl) propyl, 3- (Cyclopentyl) propyl, 3- (CyclohexyI) propyl, 3- (Cycloheptyl) propyI, 3- (Cyclooctyl) propyl, 4- (Cyclopropyl) butyl, 4- (Cyclobutyl) butyl, 4 - (Cyclopentyl) butyl, 4- (cyclohexyl) butyl, 4- (cycloheptyl) butyl, 4- (cyclooctyl) butyl;
C C4-Alkoxy-C C -alkyl: für Cι-C -Alkyl, welches mit C C4-Alkoxy substituiert ist, z.B. für Methoxymethyl, Ethoxymethyl, 1- oder 2-Methoxyethyl, 1- oder 2- Ethoxyethyl, 1-, 2- oder 3-Methoxypropyl;CC 4 -alkoxy-C C -alkyl: for -C-C alkyl which is substituted by CC 4 -alkoxy, for example for methoxymethyl, ethoxymethyl, 1- or 2-methoxyethyl, 1- or 2-ethoxyethyl, 1-, 2nd - or 3-methoxypropyl;
- C QrAlkoxy-Crd-alkoxy: für d-d-Alkoxy, welches mit C C4-Alkoxy substituiert ist, z.B. für Methoxymethoxy, Ethoxymethoxy, 1- oder 2-Methoxyethoxy, 1- oder 2-Ethoxyethoxy, 1-, 2- oder 3-Methoxypropoxy;- C Qralkoxy-Crd-alkoxy: for dd-alkoxy which is substituted by CC 4 -alkoxy, for example for methoxymethoxy, ethoxymethoxy, 1- or 2-methoxyethoxy, 1- or 2-ethoxyethoxy, 1-, 2- or 3- methoxypropoxy;
Phenyl-CrC6-alkyl: für C C6-Alkyl, welches mit Phenyl substituiert ist, z.B. für Benzyl, 1- oder 2-Phenylethyl, 1-, 2- oder 3-PhenylpropyI;Phenyl-CrC 6 -alkyl: for CC 6 -alkyl which is substituted by phenyl, for example for benzyl, 1- or 2-phenylethyl, 1-, 2- or 3-phenylpropyI;
Phenyloxy-Cι-C6-alkyl: für C C6-Alkyl, welches mit Phenoxy, substituiert ist, z.B. für Phenoxymethyl, 1- oder 2-Phenoxyethyl, 1-, 2- oder 3-Phenoxypropyl;Phenyloxy -CC 6 alkyl: for CC 6 alkyl which is substituted with phenoxy, for example for phenoxymethyl, 1- or 2-phenoxyethyl, 1-, 2- or 3-phenoxypropyl;
- Phenyl-C2-C6-alkenyl: für C2-C6-Alkenyl, welches mit Phenyl, substituiert ist, z.B. für 1- oder 2-Phenylethenyl, 1-Phenylprop-2-en-1-yl, 3-Phenyl-1-propen-1-yI, 3- Phenyl-2-propen-1-yl, 4-Phenyl-1-buten-1-yl oder 4-Phenyl-2-buten-1-yl;Phenyl-C 2 -C 6 -alkenyl: for C 2 -C 6 -alkenyl which is substituted with phenyl, for example for 1- or 2-phenylethenyl, 1-phenylprop-2-en-1-yl, 3- Phenyl-1-propen-1-yl, 3-phenyl-2-propen-1-yl, 4-phenyl-1-buten-1-yl or 4-phenyl-2-buten-1-yl;
Phenyloxy-C2-C6-alkenyl: für C2-C6-Alkenyl, welches mit Phenoxy, substituiert ist, z.B. für 1- oder 2-Phenyloxyethenyl, 1-Phenyloxyprop-2-en-1-yl, 3-Phenyloxy-1- propen-1-yl, 3-Phenyloxy-2-propen-1-yl, 4-Phenyloxy-1-buten-1-yl oder 4- Phenyloxy-2-buten-1 -yl;Phenyloxy-C 2 -C 6 alkenyl: for C 2 -C 6 alkenyl which is substituted with phenoxy, for example for 1- or 2-phenyloxyethenyl, 1-phenyloxyprop-2-en-1-yl, 3-phenyloxy -1-propen-1-yl, 3-phenyloxy-2-propen-1-yl, 4-phenyloxy-1-buten-1-yl or 4-phenyloxy-2-buten-1-yl;
Phenyl-C2-C6-alkinyl: für C2-C6-Alkinyl, welches mit Phenyl, substituiert ist, z.B. für 1-Phenylprop-2-in-1-yl, 3-Phenyl-1-propin-1-yl, 3-Phenyl-2-propin-1-yl, 4- Phenyl-1-butin-1-yl oder 4-Phenyl-2-butin-1-yl;Phenyl-C 2 -C 6 -alkynyl: for C 2 -C 6 -alkynyl which is substituted with phenyl, for example for 1-phenylprop-2-yn-1-yl, 3-phenyl-1-propyne-1- yl, 3-phenyl-2-propin-1-yl, 4- Phenyl-1-butin-1-yl or 4-phenyl-2-butin-1-yl;
Phenyloxy-C2-C6-alkinyl: für C2-C6-Alkinyl, welches mit Phenoxy, substituiert ist, z.B. für 1-Phenyloxyprop-2-in-1-yl, 3-Phenyloxy-1-propin-1-yl, 3-Phenyloxy-2- propin-1-yl, 4-Phenyloxy-1-butin-1-yl oder 4-Phenyloxy-2-butin-1-yl.Phenyloxy-C 2 -C 6 -alkynyl: for C 2 -C 6 -alkynyl which is substituted by phenoxy, for example for 1-phenyloxyprop-2-in-1-yl, 3-phenyloxy-1-propin-1- yl, 3-phenyloxy-2-propin-1-yl, 4-phenyloxy-1-butyn-1-yl or 4-phenyloxy-2-butyn-1-yl.
Im Hinblick auf die fungizide Wirksamkeit sind Anilide der allgemeinen Formel I bevorzugt, worin die Variablen R1 bis R6 unabhängig voneinander und insbesondere in Kombination die folgenden Bedeutungen aufweisen:With regard to the fungicidal activity, anilides of the general formula I are preferred in which the variables R 1 to R 6 have the following meanings independently of one another and in particular in combination:
R1, R2, R3 unabhängig voneinander Wasserstoff, Halogen, C C4-Alkyl oder C C4- Halogenalkyl. Insbesondere stehen 1 , 2 oder bevorzugt alle Reste R1, R2 und R3 für Wasserstoff;R 1 , R 2 , R 3 independently of one another are hydrogen, halogen, CC 4 -alkyl or CC 4 - haloalkyl. In particular, 1, 2 or preferably all of the radicals R 1 , R 2 and R 3 are hydrogen;
R4 Wasserstoff, Methyl, OH oder Methoxy, insbesondere Wasserstoff;R 4 is hydrogen, methyl, OH or methoxy, especially hydrogen;
R5 eine der folgenden Bedeutungen:R 5 has one of the following meanings:
- unsubstituiertes C4-C12-Aikyl, C3-Cι2-CycIoalkyl, C2-C12-Alkenyl, C5-unsubstituted C 4 -C 12 -alkyl, C 3 -C 2 -cycloalkyl, C 2 -C 12 -alkenyl, C 5 -
C12-CycIoalkenyI, C2-C12-Alkinyl, wobei die Wasserstoffatome in den 4 zuletzt genannten Gruppen teilweise oder vollständig durch Halogen substituiert sein können und die Wasserstoffatome in C3-C12- Cycloalkyl teilweise oder vollständig durch C C4-Alkyl substituiert sein können;C 12 -CycIoalkenyI, C 2 -C 12 alkynyl, where the hydrogen atoms in the last 4 groups may be partially or completely substituted by halogen and the hydrogen atoms in C 3 -C 12 cycloalkyl may be partially or completely substituted by CC 4 alkyl could be;
CrC12-Halogenalkyl, insbesondere C C4-Fluoralkyl, Crd-Alkoxy-Cr C4-alkyl, Crd-Halogenalkoxy-Crd-alkyl, insbesondere C C4- Fluoralkoxy-C C4-alkyl;CrC 12 haloalkyl, in particular CC 4 fluoroalkyl, Crd-alkoxy-Cr C 4 alkyl, Crd-haloalkoxy-Crd alkyl, in particular CC 4 - fluoroalkoxy-C C 4 alkyl;
Phenyl, Phenyl-d-Ce-alkyl, wobei der Phenylring mit 1 , 2, 3 oder 4 Resten R7 substituiert sein kann und insbesondere 0, 1 , 2 oder 3 Reste R7 aufweist; oderPhenyl, phenyl-d-Ce-alkyl, where the phenyl ring can be substituted with 1, 2, 3 or 4 radicals R 7 and in particular has 0, 1, 2 or 3 radicals R 7 ; or
- -C(C C4-Alkyl)=NO-R8, wobei die Wasserstoffatome der C C4-- -C (CC 4 -alkyl) = NO-R 8 , the hydrogen atoms of the CC 4 -
Alkylgruppe teilweise, z.B. 1-, 2- oder 3-fach oder vollständig durch Halogen substituiert sein können; und R6 unabhängig voneinander: C C4-Alkyl, C C4-Alkoxy, C C -Halogenalkyl,Alkyl group can be partially, for example 1-, 2- or 3-fold or completely substituted by halogen; and R 6 independently of one another: CC 4 -alkyl, CC 4 -alkoxy, CC -haloalkyl,
CrC4-Halogenalkoxy, oder Halogen, speziell Fluor, Chlor, Methyl, Trifluor- methyl, Methoxy, Trifluormethoxy oder Difluormethyl.CrC 4 haloalkoxy, or halogen, especially fluorine, chlorine, methyl, trifluoromethyl, methoxy, trifluoromethoxy or difluoromethyl.
Die Variable R7 ist insbesondere ausgewählt unter C C4-Alkyl, C C4-Alkoxy, C C4- Halogenalkyl, C C4-Halogenalkoxy, Nitro, CN oder Halogen, speziell Fluor, Chlor, Methyl, Trifluormethyl, Methoxy, Trifluormethoxy oder Difluormethyl.The variable R 7 is selected in particular from 4 alkyl CC, CC 4 -alkoxy, CC 4 - haloalkyl, CC 4 -haloalkoxy, nitro, CN or halogen, especially fluorine, chlorine, methyl, trifluoromethyl, methoxy, trifluoromethoxy or difluoromethyl.
Die Variable R8 ist vorzugsweise ausgewählt unter C C4-Alkyl, C3-C6- Cycloalkyl, C C4-Alkoxy, C2-C4-Alkenyl, C2-C -Alkinyl, wobei die Wasserstoffatome in diesen 5 Gruppen teilweise oder vollständig durch Halogen substituiert sein können, Halogen, Nitro, CN, Phenyl, das 1 , 2, 3 oder 4 der unter R6 genannten Gruppen aufweisen kann, Phenoxy, das 1 , 2, 3 oder 4 der unter R6 genannten Gruppen aufweisen kann, d-Ce-Alkyl- phenyl, wobei die Wasserstoffatome des Alkylteils teilweise oder vollständig durch Ha- logen substituiert sein können und der Phenylring 1 , 2, 3 oder 4 der unter R6 genannten Gruppen aufweisen kann, insbesondere unter C C4-Alkyl, C3-C6- Cycloalkyl, C2-C - Alkenyl, C2-C4-Alkinyl, wobei die Wasserstoffatome in diesen 4 Gruppen teilweise oder vollständig durch Halogen substituiert sein können, Phenyl oder Benzyl, wobei Phenyl in den zwei letztgenannten Resten 1 , 2 oder 3 der unter R6 genannten Gruppen auf- weisen kann.The variable R 8 is preferably selected from CC 4 alkyl, C 3 -C 6 cycloalkyl, CC 4 alkoxy, C 2 -C 4 alkenyl, C 2 -C alkynyl, the hydrogen atoms in these 5 groups being partially or may be completely substituted by halogen, halogen, nitro, CN, phenyl which may have 1, 2, 3 or 4 of the groups mentioned under R 6 , phenoxy which may have 1, 2, 3 or 4 of the groups mentioned under R 6 , d-Ce-alkylphenyl, where the hydrogen atoms of the alkyl part can be partially or completely substituted by halogen and the phenyl ring can have 1, 2, 3 or 4 of the groups mentioned under R 6 , in particular under CC 4 alkyl, C 3 -C 6 cycloalkyl, C 2 -C alkenyl, C 2 -C 4 alkynyl, where the hydrogen atoms in these 4 groups can be partially or completely substituted by halogen, phenyl or benzyl, phenyl in the latter two radicals 1, 2 or 3 of the groups mentioned under R 6 can have.
Im Hinblick auf ihre fungizide Wirksamkeit sind solche Anilide der Formel I bevorzugt, worin n = 0 ist.With regard to their fungicidal activity, preference is given to those anilides of the formula I in which n = 0.
Die Variable W steht insbesondere für Sauerstoff.The variable W stands in particular for oxygen.
Im Hinblick auf die fungizide Wirksamkeit der Anilide I, steht X in Formel I für eine direkte Bindung oder Sauerstoff. In einer ersten besonders bevorzugten Ausführungsform der Erfindung steht X für Sauerstoff. In einer anderen besonders bevorzugten Ausführungsform steht X für eine direkte Bindung. Sofern R5 für unsubstituiertes Alkyl steht, ist X insbesondere eine direkte Bindung.With regard to the fungicidal activity of the anilides I, X in formula I represents a direct bond or oxygen. In a first particularly preferred embodiment of the invention, X stands for oxygen. In another particularly preferred embodiment, X stands for a direct bond. If R 5 is unsubstituted alkyl, X is in particular a direct bond.
Im Hinblick auf ihre fungizide Wirksamkeit sind solche Anilide der Formel I bevorzugt, in denen die Gruppe X-R5 in ortho- oder meta-Position und insbesondere in ortho- Position zum Amidstickstoff gebunden ist. Hierunter sind besonders diejenigen Anilide der Formel I bevorzugt, in denen R1, R2 und R3 jeweils für Wasserstoff stehen, und speziell solche mit n = 0. Hierunter sind solche Anilide besonders bevorzugt, in denen R5 eine der folgenenden Bedeutungen aufweist. unsubstituiertes C4-C12-Alkyl, C3-C12-Cycloalkyl, C2-C12-Alkenyl, C5-C12- Cycloalkenyl, C2-C12-Alkinyl, wobei die Wasserstoffatome in den 4 zuletzt genannten Gruppen teilweise oder vollständig durch Halogen substituiert sein können und die Wasserstoffatome in C3-C12-Cycloalkyl teilweise oder vollständig durch CrC4-Alkyl substituiert sein können;With regard to their fungicidal activity, those anilides of the formula I are preferred in which the group XR 5 is bonded in the ortho or meta position and in particular in the ortho position to the amide nitrogen. Among these, particular preference is given to those anilides of the formula I in which R 1 , R 2 and R 3 each represent hydrogen, and especially those with n = 0. Among these, those anilides in which R 5 has one of the following meanings are particularly preferred. unsubstituted C 4 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 12 alkenyl, C 5 -C 12 cycloalkenyl, C 2 -C 12 alkynyl, the hydrogen atoms in the last 4 groups mentioned can be partially or completely substituted by halogen and the hydrogen atoms in C 3 -C 12 cycloalkyl can be partially or completely substituted by CrC 4 alkyl;
Cι-C12-Halogenalkyl, insbesondere C C4-Fluoralkyl, d-C4-Alkoxy-d-C -alkyl, C C4-Halogenalkoxy-CrC4-alkyl, insbesondere C C4-Fluoralkoxy-C C -alkyl;-C-C 12 haloalkyl, in particular CC 4 fluoroalkyl, dC 4 alkoxy-dC alkyl, CC 4 haloalkoxy-C r C 4 alkyl, especially CC 4 fluoroalkoxy C C alkyl;
Phenyl, Phenyl-CrC6-alkyl, wobei der Phenylring mit 1, 2, 3 oder 4 Resten R7 substituiert sein kann und insbesondere 0, 1 , 2 oder 3 Reste R7 aufweist; oderPhenyl, phenyl-CrC 6 -alkyl, where the phenyl ring can be substituted by 1, 2, 3 or 4 radicals R 7 and in particular has 0, 1, 2 or 3 radicals R 7 ; or
-C(CrC4-Alkyl)=NO-R8, wobei die Wasserstoffatome der d-C4-Alkylgruppe teilweise oder vollständig durch Halogen substituiert sein können.-C (CrC 4 alkyl) = NO-R 8 , where the hydrogen atoms of the dC 4 alkyl group can be partially or completely substituted by halogen.
Hierbei haben R7 und R8 insbesondere die als bevorzugt angegebenen Bedeutungen, W steht insbesondere für Sauerstoff.Here R 7 and R 8 have in particular the meanings given as preferred, W in particular represents oxygen.
Insbesondere sind im Hinblick auf ihre Verwendung als Fungizide und Wirkstoffe zur Bekämpfung von Schädlingen die in den folgenden Tabelle 1 bis 6 zusammengestellten Einzelverbindungen bevorzugt, die unter die allgemeinen Formeln la, Ib und Ic fallen, wobei Verbindungen der allgemeinen Formel la besonders bevorzugt sind.In particular, with regard to their use as fungicides and active compounds for controlling pests, the individual compounds listed in Tables 1 to 6 below, which come under the general formulas Ia, Ib and Ic, are preferred, compounds of the general formula Ia being particularly preferred.
Tabelle ATable A
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Tabelle 1:
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Table 1:
Verbindungen der allgemeinen Formel la;Compounds of the general formula Ia;
Figure imgf000025_0001
Figure imgf000025_0001
worin X eine direkte Bindung ist und R5 eine in Tabelle A angegebene Bedeutung aufweist.wherein X is a direct bond and R 5 has a meaning given in Table A.
Tabelle 2:Table 2:
Verbindungen der allgemeinen Formel la, worin X für O steht und R5 eine in der Tabelle A angegebene Bedeutung aufweist.Compounds of the general formula Ia, in which X is O and R 5 has the meaning given in Table A.
Tabelle 3:Table 3:
Verbindungen der allgemeinen Formel Ib,Compounds of the general formula Ib,
Figure imgf000025_0002
Figure imgf000025_0002
worin X eine direkte Bindung ist und R5 eine in der Tabelle A angegebene Bedeutung aufweist.wherein X is a direct bond and R 5 has a meaning given in Table A.
Tabelle 4:Table 4:
Verbindungen der allgemeinen Formel Ib, worin X für O steht und R5 eine in der Tabel- Ie A angegebene Bedeutung aufweist.Compounds of the general formula Ib, in which X is O and R 5 has the meaning given in Table Ie A.
Tabelle 5:Table 5:
Verbindungen der allgemeinen Formel Ic,
Figure imgf000026_0001
Compounds of the general formula Ic,
Figure imgf000026_0001
worin X eine direkte Bindung ist und R5eine in der Tabelle A angegebene Bedeutung aufweist.wherein X is a direct bond and R 5 has a meaning given in Table A.
Tabelle 6:Table 6:
Verbindungen der allgemeinen Formel Ic, worin X für O steht und R5eine in der Tabelle A angegebene Bedeutung aufweist.Compounds of the general formula Ic, in which X is O and R 5 has the meaning given in Table A.
Die 3-Trifluormethylpicolinsäureanilide der allgemeinen Formel I mit W = O und R4 = H können gemäß der in Schema 1 gezeigten Synthese nach literaturbekannten Verfahren durch Umsetzung aktivierter 3-Trifluormethylpicolinsäurederivate der allgemeinen Formel II mit einem Anilin III hergestellt werden [Houben-Weyl: „Methoden der organ. Chemie", Georg-Thieme-Verlag, Stuttgart, New York 1985, Band E5, S. 941-1045.]. Aktivierte Carbonsäurederivate sind beispielsweise Halogenide, Aktivester, Anhydride, Azide, z.B. Chloride, Fluoride, Bromide, para-Nitrophenylester, Pentafluorphenylester, N-Hydroxysuccinimidester und Hydroxybenzotriazol-1-yl-ester.The 3-trifluoromethylpicolinic acid anilides of the general formula I with W = O and R 4 = H can be prepared by reacting activated 3-trifluoromethylpicolinic acid derivatives of the general formula II with an aniline III according to the synthesis shown in Scheme 1 [Houben-Weyl: " Methods of organ. Chemie ", Georg-Thieme-Verlag, Stuttgart, New York 1985, Volume E5, pp. 941-1045.]. Activated carboxylic acid derivatives are, for example, halides, active esters, anhydrides, azides, for example chlorides, fluorides, bromides, para-nitrophenyl esters, pentafluorophenyl esters , N-hydroxysuccinimide ester and hydroxybenzotriazol-1-yl ester.
Schema 1 :Scheme 1:
Figure imgf000026_0002
Figure imgf000026_0002
(II) (III) (I)(II) (III) (I)
In Schema 1 steht L für eine geeignete nucleophil verdrängbare Abgangsgruppe, beispielsweise für Halogenid, Aktivester-Rest, einen Anhydrid-Rest, Azid, z.B. Chlorid, Fluorid, Bromid, para-Nitrophenyloxy, Pentafluorphenyloxy, einen von N- Hydroxysuccinimid oder von Hydroxybenzotriazol-1-yl abgeleiteten Rest. Die 3-Trifluormethylpicolinsäureanilide der allgemeinen Formel I können außerdem durch Umsetzung der freien Säuren lla mit einem gegebenenfalls N-substituierten Anilin lila in Gegenwart eines Kupplungsreagenzes hergestellt werden (Schema 2).In Scheme 1, L represents a suitable nucleophilically displaceable leaving group, for example halide, active ester residue, an anhydride residue, azide, for example chloride, fluoride, bromide, para-nitrophenyloxy, pentafluorophenyloxy, one of N-hydroxysuccinimide or of hydroxybenzotriazole-1 -yl derived rest. The 3-trifluoromethylpicolinic acid anilides of the general formula I can also be prepared by reacting the free acids IIIa with an optionally N-substituted aniline purple in the presence of a coupling reagent (Scheme 2).
Schema 2:Scheme 2:
Figure imgf000027_0001
Figure imgf000027_0001
(lla) (lila) (l) {Y = O}(lla) (purple) (l) {Y = O}
Kupplungsreagenzien können beispielsweise sein:Coupling reagents can be, for example:
Kupplungsreagenzien auf Carbodiimid-Basis, z.B. N,N'-DicycIohexylcarbodiimid [J.C. Sheehan, G.P. Hess, J. Am. Chem. Soc. 1955, 77, 1067], N-(3-Coupling reagents based on carbodiimide, e.g. N, N'-dicyclohexylcarbodiimide [J.C. Sheehan, G.P. Hess, J. Am. Chem. Soc. 1955, 77, 1067], N- (3-
Dimethylaminopropyl)-N'-ethyI-carbodiimid;Dimethylaminopropyl) -N'-ethyl-carbodiimide;
Kupplungsreagenzien, die gemischte Anhydride mit Kohlensäureestern bilden, z.B. 2-Ethoxy-1-ethoxycarbonyl-1,2-dihydrochinolin [B. Belleau, G. Malek, J. A- mer. Chem. Soc. 1968, 90, 1651.], 2-iso-Butyloxy-1-iso-butyloxycarbonyl-1 ,2- dihydrochinolin [Y. Kiso, H. Yajima, J. Chem. Soc, Chem. Commun. 1972, 942.];Coupling reagents that form mixed anhydrides with carbonic acid esters, e.g. 2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline [B. Belleau, G. Malek, J. Amer. Chem. Soc. 1968, 90, 1651.], 2-iso-butyloxy-1-iso-butyloxycarbonyl-1, 2-dihydroquinoline [Y. Kiso, H. Yajima, J. Chem. Soc, Chem. Commun. 1972, 942.];
Kupplungsreagenzien aus Phosphonium-Basis, z.B. (BenzotriazoM-yloxy)-tris- (dimethylamino)-phosophonium-hexafluorophosphat [B. Castro, J.R. Domoy, G. Evin, C. Selve, Tetrahedron Lett. 1975, 14, 1219.], (Benzotriazol-1 -yl-oxy)- tripyrrolidinophosphonium-hexafluorophosphat [J. Coste et.al., Tetrahedron Lett. 1990, 31 , 205.];Phosphonium-based coupling reagents, e.g. (BenzotriazoM-yloxy) tris- (dimethylamino) -phosphonium hexafluorophosphate [B. Castro, J.R. Domoy, G. Evin, C. Selve, Tetrahedron Lett. 1975, 14, 1219.], (Benzotriazol-1-yloxy) - tripyrrolidinophosphonium hexafluorophosphate [J. Coste et.al., Tetrahedron Lett. 1990, 31, 205.];
Kupplungsreagenzien auf Uroniumbasis bzw. mit Guanidinium-N-oxid-Struktur, z.B. N,N,N',N'-Tetramethyl-O-(1H-benzotriazol-1-yl)-uronium-hexafluorophosphat [R. Knorr, A. Trzeciak, W. Bannwarth, D. Gillessen, Tetrahedron Lett. 1989, 30, 1927. ], N,N,N',N'-Tetramethyl-O-(benzotriazol-1-yl)-uronium-tetrafluoroborat, (Benzotriazol-l-yloxy)-dipiperidinocarbenium-hexafluorophosphat [S. Chen, J.Coupling reagents based on uronium or with guanidinium N-oxide structure, e.g. N, N, N ', N'-tetramethyl-O- (1H-benzotriazol-1-yl) uronium hexafluorophosphate [R. Knorr, A. Trzeciak, W. Bannwarth, D. Gillessen, Tetrahedron Lett. 1989, 30, 1927.], N, N, N ', N'-tetramethyl-O- (benzotriazol-1-yl) uronium tetrafluoroborate, (benzotriazol-l-yloxy) dipiperidinocarbenium hexafluorophosphate [S. Chen, J.
Xu, Tetrahedron Lett. 1992, 33, 647.];Xu, Tetrahedron Lett. 1992, 33, 647.];
Kupplungsreagenzien.die Säurechloride bilden, z.B. Phosphorsäure-bis-(2-oxo- oxazo!idid)-chlorid [J. Diago-Mesequer, Synthesis 1980, 547.].Coupling reagents that form acid chlorides, e.g. Phosphoric acid bis (2-oxo-oxazo! Idid) chloride [J. Diago-Mesequer, Synthesis 1980, 547.].
Die 3-Trifluormethylpicolinsäureanilide der allgemeinen Formel I mit R4 = ggf. mit Halogen substituiertem Alkyl oder ggf. mit Halogen substituiertem Cycloalkyl können durch Alkylierung der Amide I (worin R4 = Wasserstoff ist und die gemäß Schema .1 oder 2 zugänglich sind) mit geeigneten Alkylierungsreagenzien in Gegenwart von Basen her- gestellt werden. Verfahren hierzu sind bekannt, z.B. aus J. Am. Chem. Soc. 1952, 74, S.3121 , Helv. Chim. Acta, 1974, 57, S 281, Synth. Commun. 1988, 18, S. 2011.The 3-trifluoromethylpicolinic acid anilides of the general formula I with R 4 = optionally halogen-substituted alkyl or optionally halogen-substituted cycloalkyl can by alkylating the amides I (in which R 4 = hydrogen and which are accessible according to Scheme .1 or 2) with suitable alkylation reagents in the presence of bases be put. Methods for this are known, for example from J. Am. Chem. Soc. 1952, 74, p.3121, Helv. Chim. Acta, 1974, 57, p. 281, synth. Commun. 1988, 18, p. 2011.
Die 3-Trifluormethylpicolinsäuren lla können nach literaturbekannten Methoden hergestellt werden z.B. aus den entsprechenden Pyridin-2,3-dicarbonsäuren durch Umsetzung mit Schwefeltetrafluorid in Anlehnung an die in J. Fluorine Chem. 1993, 60, S. 233-237; JP 1980-5059135; US 4803205; oder Khim. Geterotsikl. Soedin 1994, S. 657- 659; oder durch Einführung der Carboxylgruppe nach der in Eur. J. Org. Chem. 2002, S. 327-330.The 3-trifluoromethylpicolinic acids IIIa can be prepared by methods known from the literature, e.g. from the corresponding pyridine-2,3-dicarboxylic acids by reaction with sulfur tetrafluoride based on that described in J. Fluorine Chem. 1993, 60, pp. 233-237; JP 1980-5059135; US 4803205; or khim. Geterotsikl. Soedin 1994, pp. 657-659; or by introducing the carboxyl group according to the in Eur. J. Org. Chem. 2002, pp. 327-330.
Daraus sind die aktivierten Thiophencarbonsäurederivate II nach literaturbekannten Verfahren synthetisierbar [Houben-Weyl: „Methoden der organ. Chemie", Georg- Thieme-Verlag, Stuttgart, New York 1985, Band E5, S. 587-614, 633-772.]The activated thiophenecarboxylic acid derivatives II can be synthesized therefrom by methods known from the literature [Houben-Weyl: “Methods of organ. Chemistry ", Georg Thieme Verlag, Stuttgart, New York 1985, Volume E5, pp. 587-614, 633-772.]
Die Aniline III und lila sind nach literaturbekannten Methoden synthetisierbar [Houben- Weyl: „Methoden der organ. Chemie", Georg-Thieme-Verlag, Stuttgart, New York, Band XI, Teil 1, S. 9-1005.]Anilines III and lilac can be synthesized using methods known from the literature [Houben-Weyl: “Methods of organ. Chemistry ", Georg Thieme Verlag, Stuttgart, New York, Volume XI, Part 1, pp. 9-1005.]
3-Trifluormethylpicolinthioanilide der allgemeinen Formel I mit W = S können durch allgemein bekannte Schwefelungsverfahren aus den entsprechenden Aniliden der Formel I mitX = O hergestellt werden, beispielsweise durch Schwefelung mit P2S5 nach J. Am. Chem. Soc. 1951, 73, S. 4988, durch Umsetzung mit Lawessons Reagenz nach Heterocycles 2002, 58, S. 203-212; oder Pharmazie 1999, 54 (9), S.645-650.3-trifluoromethylpicolinthioanilides of the general formula I with W = S can be prepared by generally known sulfurization processes from the corresponding anilides of the formula I with X = O, for example by sulfurization with P 2 S 5 according to J. Am. Chem. Soc. 1951, 73, p. 4988, by reaction with Lawesson's reagent according to Heterocycles 2002, 58, p. 203-212; or Pharmazie 1999, 54 (9), p.645-650.
Die 3-Trifluormethylpicolinsäureanilide der allgemeinen Formel I und ihre landwirtschaftlich verträglichen, d.h. brauchbaren Salze eignen sich als Fungizide. Sie zeichnen sich durch eine hervorragende Wirksamkeit gegen ein breites Spektrum von pflan- zenpathogenen Pilzen, insbesondere aus der Klasse der Ascomyceten, Deuteromyce- ten, Phycomyceten und Basidiomyceten, aus. Sie sind zum Teil systemisch wirksam und können im Pflanzenschutz als Blatt- und Bodenfungizide eingesetzt werden.The 3-trifluoromethylpicolinic acid anilides of the general formula I and their agriculturally compatible, i.e. usable salts are suitable as fungicides. They are characterized by excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some of them are systemically effective and can be used in plant protection as leaf and soil fungicides.
Besondere Bedeutung haben sie für die Bekämpfung einer Vielzahl von Pilzen an verschiedenen Kulturpflanzen wie Weizen, Roggen, Gerste, Hafer, Reis, Mais, Gras, Bananen, Baumwolle, Soja, Kaffee, Zuckerrohr, Wein, Obst- und Zierpflanzen und Gemü- sepflanzen wie Gurken, Bohnen, Tomaten, Kartoffeln und Kürbisgewächsen, sowie an den Samen dieser Pflanzen.They are of particular importance for combating a large number of fungi on various crops such as wheat, rye, barley, oats, rice, corn, grass, bananas, cotton, soybeans, coffee, sugar cane, wine, fruit and ornamental plants and vegetable plants such as Cucumbers, beans, tomatoes, potatoes and squash, as well as on the seeds of these plants.
Speziell eignen sie sich zur Bekämpfung folgender Pflanzenkrankheiten:They are particularly suitable for combating the following plant diseases:
• Altern aria- Arten an Gemüse und Obst, • Botrytis cinerea (Grauschimmel) an Erdbeeren, Gemüse, Zierpflanzen und Reben,• aging aria types of vegetables and fruits, Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and vines,
Cercospora arachidicola an Erdnüssen,Cercospora arachidicola on peanuts,
Erysiphe cichoracearum und Sphaerotheca fuliginea an Kürbisgewächsen,Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants,
Erysiphe graminis (echter Mehltau) an Getreide,Erysiphe graminis (powdery mildew) on cereals,
Fusarium- und Verticillium-Arten an verschiedenen Pflanzen,Fusarium and Verticillium species on different plants,
Helminthosporium-Arten an Getreide,Helminthosporium species on cereals,
Mycosphaerella-Arten an Bananen und Erdnüssen,Mycosphaerella species on bananas and peanuts,
Phytophthora infestans an Kartoffeln und Tomaten, • Plasmopara viticola an Reben,Phytophthora infestans on potatoes and tomatoes, • Plasmopara viticola on vines,
Podosphaera leucotricha an Äpfeln,Podosphaera leucotricha on apples,
Pseudocercosporella herpotrichoides an Weizen und Gerste,Pseudocercosporella herpotrichoides on wheat and barley,
Pseudoperonospora-Arten an Hopfen und Gurken,Pseudoperonospora species on hops and cucumbers,
Puccinia-Arten an Getreide, • Pyricularia oryzae an Reis,Puccinia species on cereals, • Pyricularia oryzae on rice,
Rhizoctonia-Arten an Baumwolle, Reis und Rasen,Rhizoctonia species on cotton, rice and lawn,
Septoria nodorum an Weizen,Septoria nodorum on wheat,
Sphaerotheca fuliginea (Gurkenmehltau) an Gurken,Sphaerotheca fuliginea (cucumber mildew) on cucumber,
Uncinula necator an Reben, • Ustilago-Arten an Getreide und Zuckerrohr, sowieUncinula necator on vines, • Ustilago species on cereals and sugar cane, as well
Venturia-Arten (Schorf) an Äpfeln und Birnen.Venturia species (scab) on apples and pears.
Septoria TriticiSeptoria Tritici
Pyrenophora-ArtenPyrenophora species
Leptosphaeria Nodorum • Rhynchosporium-ArtenLeptosphaeria Nodorum • Rhynchosporium species
Typhula-ArtenTyphula species
Die Verbindungen der Formel I eignen sich außerdem zur Bekämpfung von Schadpilzen wie Paecilomyces variotii im Materialschutz (z.B. Holz, Papier, Dispersionen für den Anstrich, Fasern bzw. Gewebe) und im Vorratsschutz.The compounds of the formula I are also suitable for combating harmful fungi such as Paecilomyces variotii in the protection of materials (e.g. wood, paper, dispersions for painting, fibers or fabrics) and in the protection of stored products.
Die Verbindungen der Formel I werden angewendet, indem man die Pilze oder die vor Pilzbefall zu schützenden Pflanzen, Saatgüter, Materialien oder den Erdboden mit einer fungizid wirksamen Menge der Wirkstoffe behandelt. Die Anwendung kann sowohl vor als auch nach der Infektion der Materialien, Pflanzen oder Samen durch die Pilze erfolgen. Die fungiziden Mittel enthalten im allgemeinen zwischen 0,1 und 95, vorzugsweise zwischen 0,5 und 90 Gew.-% Wirkstoff.The compounds of the formula I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally active amount of the active compounds. The application can take place both before and after the infection of the materials, plants or seeds by the fungi. The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active ingredient.
Die Aufwandmengen liegen bei der Anwendung im Pflanzenschutz je nach Art des gewünschten Effektes zwischen 0,01 und 2,0 kg Wirkstoff pro ha.Depending on the type of effect desired, the application rates in crop protection are between 0.01 and 2.0 kg of active ingredient per ha.
Bei der Saatgutbehandlung werden im allgemeinen Wirkstoffmengen von 0,001 bis 0,1 g, vorzugsweise 0,01 bis 0,05 g je Kilogramm Saatgut benötigt.In the case of seed treatment, amounts of active ingredient of 0.001 to 0.1 g, preferably 0.01 to 0.05 g, per kg of seed are generally required.
Bei der Anwendung im Material- bzw. Vorratsschutz richtet sich die Aufwandmenge an Wirkstoff nach der Art des Einsatzgebietes und des gewünschten Effekts. Übliche Aufwandmengen sind im Materialschutz beispielsweise 0,001 g bis 2 kg, vorzugsweise 0,005 g bis 1 kg Wirkstoff pro Qubikmeter behandelten Materials.When used in material or stock protection, the amount of active ingredient applied depends on the type of application and the desired effect. Usual application rates in material protection are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active ingredient per cubic meter of treated material.
Die Verbindungen der Formel I können in die üblichen Formulierungen überführt werden, z.B. Lösungen, Emulsionen, Suspensionen, Stäube, Pulver, Pasten und Granulate. Die Anwendungsform richtet sich nach dem jeweiligen Verwendungszweck; sie soll in jedem Fall eine feine und gleichmäßige Verteilung der erfindungsgemäßen Verbindung gewährleisten.The compounds of formula I can be converted into the usual formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules. The form of application depends on the respective purpose; in any case, it should ensure a fine and uniform distribution of the compound according to the invention.
Die Formulierungen werden in bekannter Weise hergestellt, z.B. durch Verstrecken des Wirkstoffs mit Lösungsmitteln und/oder Trägerstoffen, gewünschtenfalls unter Verwendung von Emulgiermitteln und Dispergiermitteln, wobei im Falle von Wasser als Verdünnungsmittel auch andere organische Lösungsmittel als Hilfslösungsmittel verwen- det werden können. Als Hilfsstoffe kommen dafür im wesentlichen in Betracht: Lösungsmittel wie Aromaten (z.B. Xylol), chlorierte Aromaten (z.B. Chlorbenzole), Paraffine (z.B. Erdölfraktionen), Alkohole (z.B. Methanol, Butanol), Ketone (z.B. Cyclohexa- non), Amine (z.B.Ethanolamin, Dimethylformamid) und Wasser; Trägerstoffe wie natürliche Gesteinsmehle (z.B. Kaoline, Tonerden, Talkum, Kreide) und synthetische Ge- steinsmehle (z.B. hochdisperse Kieselsäure, Silikate); Emulgiermittel wie nichtionoge- ne und anionische Emulgatoren (z.B. Polyoxyethylen-Fettalkohol-Ether, Alkylsulfonate und Arylsulfonate) und Dispergiermittel wie Lignin-Sulfitablaugen und Methylcellulose.The formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, where in the case of water as diluent other organic solvents can also be used as auxiliary solvents. The following are essentially considered as auxiliaries: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g. ethanolamine) , Dimethylformamide) and water; Carriers such as natural powdered rock (e.g. kaolins, clays, talc, chalk) and synthetic powdered rock (e.g. highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste liquors and methyl cellulose.
Als oberflächenaktive Stoffe kommen Alkali-, Erdalkali-, Ammoniumsalze von Ligninsul- fonsäure, Naphthalinsulfonsäure, Phenolsulfonsäure, Dibutylnaphthalinsulfonsäure, Alkylarylsulfonate, Alkylsulfate, Alkylsulfonate, Fettalkoholsulfate und Fettsäuren sowie deren Alkali- und Erdalkalisalze, Salze von sulfatiertem Fettalkoholglykolether, Kondensationsprodukte von sulfoniertem Naphthalin und Naphthalinderivaten mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphtalinsulfonsäure mit Phenol und Formaldehyd, Polyoxyethylenoctylphenolether, ethoxyliertes Isooctylphe- nol, Octylphenol, Nonylphenol, Alkylphenolpolyglykolether, Tributylphenylpolyglyko- lether, Alkylarylpolyetheralkohole, Isotridecylalkohol, Fettalkoholethylenoxid- Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylenalkylether, ethoxyliertes Polyo- xypropylen, Laurylalkoholpolyglykoletheracetal, Sorbitester, Ligninsulfitablaugen und Methylcellulose in Betracht.Suitable surfactants are alkali metal, alkaline earth metal salts, sulfonic acid ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids and their alkali and alkaline earth metal salts, salts of sulfated fatty alcohol glycol ethers, condensates of sulfonated naphthalene and naphthalene derivatives with Formaldehyde, condensation products of naphthalene or naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphe- nol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbylglycol ether acetal, l-sorbylglycol ether acetal, l-sorbolglycol ether acetal, l-sorbolglycol ether acetal, l-sorbolglycol ether acetal, l-sorbolglycol ether acetal, l-sorbolglycol ether acetal, and sorbylsulfonylglycol ether acetal, l-sorbolglycol ether acetal, l-sorbyl ether glycolate, sorbitol, and / or methylglycol ether acetal, sorbate, and / or polyglycol ether acetal.
Zur Herstellung von direkt versprühbaren Lösungen, Emulsionen, Pasten oder Öldis- persionen kommen Mineralölfraktionen von mittlerem bis hohem Siedepunkt, wie Kero- sin oder Dieselöl, ferner Kohlenteeröle sowie Öle pflanzlichen oder tierischen Ur- sprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, z.B. Benzol, Toluol, Xylol, Paraffin, Tetrahydronaphthalin, alkylierte Naphthaline oder deren Derivate, Methanol, Ethanol, Propanol, Butanol, Chloroform, Tetrachlorkohlenstoff, Cyclohe- xanol, Cyclohexanon, Chlorbenzol, Isophoron, stark polare Lösungsmittel, z.B. Di- methylformamid, Dimethylsulfoxid, N-Methylpyrrolidon, Wasser, in Betracht.For the production of directly sprayable solutions, emulsions, pastes or oil dispersions, mineral oil fractions from medium to high boiling points, such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents, e.g. Dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, into consideration.
Pulver-, Streu- und Stäubemittel können durch Mischen oder gemeinsames Vermählen der wirksamen Substanzen mit einem festen Trägerstoff hergestellt werden.Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
Granulate, z.B. Umhüllungs-, Imprägnierungs- und Homogengranulate, können durch Bindung der Wirkstoffe an feste Trägerstoffe hergestellt werden. Feste Trägerstoffe sind z.B. Mineralerden, wie Silicagel, Kieselsäuren, Kieselgele, Silikate, Talkum, Kaolin, Attaclay, Kalkstein, Kalk, Kreide, Bolus, Löß, Ton, Dolomit, Diatomeenerde, Calci- um- und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Düngemittel, wie z.B. Ammoniumsulfat, Ammoniumphosphat, Ammoniumnitrat, Harnstoffe und pfianzli- ehe Produkte, wie Getreidemehl, Baumrinden-, Holz- und Nußschalenmehl, Cellulose- pulver und andere feste Trägerstoffe.Granules, e.g. Coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are e.g. Mineral soils, such as silica gel, silicas, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.
Die Formulierungen enthalten im allgemeinen zwischen 0,01 und 95 Gew.-%, vorzugsweise zwischen 0,1 und 90 Gew.-% des Wirkstoffs. Die Wirkstoffe werden dabei in einer Reinheit von 90% bis 100%, vorzugsweise 95% bis 100% (nach NMR-Spektrum) eingesetzt.The formulations generally contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight, of the active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
Beispiele für Formulierungen sind:Examples of formulations are:
I. 5 Gew.-Teile einer erfindungsgemäßen Verbindung werden mit 95 Gew.-Teilen feinteiligem Kaolin innig vermischt. Man erhält auf diese Weise ein Stäubemittel, das 5 Gew.-% des Wirkstoffs enthält.I. 5 parts by weight of a compound according to the invention are intimately mixed with 95 parts by weight of finely divided kaolin. In this way a dust is obtained which contains 5% by weight of the active ingredient.
II. 30 Gew.-Teile einer erfindungsgemäßen Verbindung werden mit einer Mischung aus 92 Gew.-Teilen pulverförmigem Kieselsäuregel und 8 Gew.-Teilen Paraffinöl, das auf die Oberfläche dieses Kieselsäuregels gesprüht wurde, innig vermischt. Man erhält auf diese Weise eine Aufbereitung des Wirkstoffs mit guter Haftfähigkeit (Wirkstoffgehalt 23 Gew.-%).II. 30 parts by weight of a compound according to the invention are mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil, that was sprayed onto the surface of this silica gel, mixed intimately. A preparation of the active ingredient with good adhesiveness (active ingredient content 23% by weight) is obtained in this way.
III. 10 Gew.-Teile einer erfindungsgemäßen Verbindung werden in einer Mischung gelöst, die aus 90 Gew.-Teilen Xylol, 6 Gew.-Teilen des Anlagerungsproduktes von 8 bis 10 Mol Ethylenoxid an 1 Mol Ölsäure-N-monoethanolamid, 2 Gew.- Teilen Calciumsalz der Dodecylbenzolsulfonsäure und 2 Gew.-Teilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Ricinusöl besteht (Wirkstoff- gehalt 9 Gew.-%).III. 10 parts by weight of a compound according to the invention are dissolved in a mixture consisting of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 2 parts by weight Calcium salt of dodecylbenzenesulfonic acid and 2 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil (active ingredient content 9% by weight).
IV. 20 Gew.-Teile einer erfindungsgemäßen Verbindung werden in einer Mischung gelöst, die aus 60 Gew.-Teilen Cyclohexanon, 30 Gew.-Teilen Isobutanol, 5 Gew.-Teilen des Anlagerungsproduktes von 7 Mol Ethylenoxid an 1 Mol Isooc- tylphenol und 5Gew.-Teilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Ricinusöl besteht (Wirkstoffgehalt 16 Gew.-%).IV. 20 parts by weight of a compound according to the invention are dissolved in a mixture consisting of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of iso-octylphenol and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil (active ingredient content 16% by weight).
V. 80 Gew.-Teile einer erfindungsgemäßen Verbindung werden mit 3 Gew.-Teilen des Natriumsalzes der Diisobutylnaphthalin-alpha-sulfonsäure, 10 Gew.-Teilen des Natriumsalzes einer Ligninsulfonsäure aus einer Sulfit-Abiauge und 7 Gew.-V. 80 parts by weight of a compound according to the invention are mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite liquor and 7 parts by weight.
Teilen pulverförmigem Kieselsäuregel gut vermischt und in einer Hammermühle vermählen (Wirkstoffgehalt 80 Gew.-%).Mix parts of the powdered silica gel well and grind them in a hammer mill (active ingredient content 80% by weight).
VI. Man vermischt 90 Gew.-Teile einer erfindungsgemäßen Verbindung mit 10 Gew.- Teilen N-Methyl-a-pyrrolidon und erhält eine Lösung, die zur Anwendung in Form kleinster Tropfen geeignet ist (Wirkstoffgehalt 90 Gew.-%).VI. 90 parts by weight of a compound according to the invention are mixed with 10 parts by weight of N-methyl-a-pyrrolidone, and a solution is obtained which is suitable for use in the form of very small drops (active substance content 90% by weight).
VII. 20 Gew.-Teile einer erfindungsgemäßen Verbindung werden in einer Mischung gelöst, die aus 40 Gew.-Teilen Cyclohexanon, 30 Gew.-Teilen Isobutanol, 20 Gew.-Teilen des Anlagerungsproduktes von 7 Mol Ethylenoxid an 1 Mol Isooc- tylphenol und 10 Gew.-Teilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Ricinusöl besteht. Durch Eingießen und feines Verteilen der Lösung in 100 000 Gew.-Teilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gew.- % des Wirkstoffs enthält.VII. 20 parts by weight of a compound according to the invention are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of iso-octylphenol and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.
VIII. 20 Gew.-Teile einer erfindungsgemäßen Verbindung werden mit 3 Gew.-Teilen des Natriumsalzes der Diisobutylnaphthalin-α-sulfonsäure, 17 Gew.-Teilen des Natriumsalzes einer Ligninsulfonsäure aus einer Sulfit-Ablauge und 60 Gew.- Teilen pulverförmigem Kieselsäuregel gut vermischt und in einer Hammermühle vermählen. Durch feines Verteilen der Mischung in 20 000 Gew.-Teilen Wasser erhält man eine Spritzbrühe, die 0,1 Gew.-% des Wirkstoffs enthält.VIII. 20 parts by weight of a compound according to the invention are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and milled in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water a spray liquor is obtained which contains 0.1% by weight of the active ingredient.
IX. 10 Gew.-Teile der erfindungsgemäßen Verbindung werden in 63 Gew.-Teilen Cyclohexanon, 27 Gew.-Teilen Dispergiermittel (beispielsweise eine Mischung aus 50 Gew.-Teilen des Anlagerungsprodukts von 7 Mol Ethylenoxid an 1 MolIX. 10 parts by weight of the compound according to the invention are in 63 parts by weight of cyclohexanone, 27 parts by weight of dispersant (for example a mixture of 50 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole
Isooctylphenol und 50 Gew.-Teilen des Anlagerungsprodukts von 40 Mol Ethylenoxid an 1 Mol Ricinusöl) gelöst. Die Stammlösung wird anschließend durch Verteilen in Wasser auf die gewünschte Konzentration verdünnt, z.B. auf eine Konzentration im Bereich von 1 bis 100 ppm.Isooctylphenol and 50 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil) dissolved. The stock solution is then diluted to the desired concentration, e.g. to a concentration in the range of 1 to 100 ppm.
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder den daraus bereiteten Anwendungsformen, z.B. in Form von direkt versprühbaren Lösungen, Pulvern, Suspensionen oder Dispersionen, Emulsionen, Oldispersionen, Pasten, Stäubemitteln, Streumitteln, Granulaten durch Versprühen, Vernebeln, Verstäuben, Verstreuen oder Gießen angewendet werden. Die Anwendungsformen richten sich ganz nach den Verwendungszwecken; sie sollten in jedem Fall möglichst die feinste Verteilung der erfindungsgemäßen Wirkstoffe gewährleisten.The active ingredients as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, old dispersions, pastes, dusts, sprinkling agents, granules by spraying, atomizing, dusting, scattering or pouring. The application forms depend entirely on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
Wäßrige Anwendungsformen können aus Emulsionskonzentraten, Pasten oder netzba- ren Pulvern (Spritzpulver, Oldispersionen) durch Zusatz von Wasser bereitet werden. Zur Herstellung von Emulsionen, Pasten oder Oldispersionen können die Substanzen als solche oder in einem Öl oder Lösungsmittel gelöst, mittels Netz-, Haft-, Dispergier- oder Emulgiermitttel in Wasser homogenisiert werden. Es können aber auch aus wirksamer Substanz Netz-, Haft-, Dispergier- oder Emulgiermittel und eventuell Lösungs- mittel oder Öl bestehende Konzentrate hergestellt werden, die zur Verdünnung mit Wasser geeignet sind.Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, old dispersions) by adding water. To prepare emulsions, pastes or old dispersions, the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, concentrates consisting of an active substance, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or oil can also be prepared which are suitable for dilution with water.
Die Wirkstoffkonzentrationen in den anwendungsfertigen Zubereitungen können in größeren Bereichen variiert werden. Im allgemeinen liegen sie zwischen 0,0001 und 10%. Häufig reichen bereits geringe Wirkstoffmengen an Verbindung I in der anwendungsfertigen Zubereitung aus, z.B. 2 bis 200 ppm. Ebenso sind anwendungsfertige Zubereitungen mit Wirkstoffkonzentrationen im Bereich von 0,01 bis 1 % bevorzugt. •The active ingredient concentrations in the ready-to-use preparations can be varied over a wide range. Generally they are between 0.0001 and 10%. Small amounts of active compound I are often sufficient in the ready-to-use preparation, e.g. 2 to 200 ppm. Ready-to-use preparations with active ingredient concentrations in the range from 0.01 to 1% are also preferred. •
Die Wirkstoffe können auch mit gutem Erfolg im Ultra-Low-Volume-Verfahren (ULV) verwendet werden, wobei es möglich ist, Formulierungen mit mehr als 95 Gew.-% Wirkstoff oder sogar den Wirkstoff ohne Zusätze auszubringen.The active ingredients can also be used with great success in the ultra-low-volume process (ULV), it being possible to apply formulations with more than 95% by weight of active ingredient or even the active ingredient without additives.
Zu den Wirkstoffen können Öle verschiedenen Typs, Herbizide, Fungizide, andere . Schädlingsbekämpfungsmittel, Bakterizide, gegebenenfalls auch erst unmittelbar vor der Anwendung (Tankmix), zugesetzt werden. Diese Mittel können zu den erfindungs- gemäßen Mitteln im Gewichtsverhältnis 1:10 bis 10:1 zugemischt werden.The active substances can include oils of various types, herbicides, fungicides, and others. Pesticides, bactericides, if necessary, only immediately before use (tank mix). These means can be added to the be mixed in a weight ratio of 1:10 to 10: 1.
Die erfindungsgemäßen Mittel können in der Anwendungsform als Fungizide auch zusammen mit anderen Wirkstoffen vorliegen, der z.B. mit Herbiziden, Insektiziden, Wachstumsregulatoren, Fungiziden oder auch mit Düngemitteln. Beim Vermischen der Verbindungen I bzw. der sie enthaltenden Mittel in der Anwendungsform als Fungizide mit anderen Fungiziden erhält man in vielen Fällen eine Vergrößerung des fungiziden Wirkungsspektrums.In the use form as fungicides, the compositions according to the invention can also be present together with other active compounds which, e.g. with herbicides, insecticides, growth regulators, fungicides or also with fertilizers. Mixing the compounds I or the compositions containing them in the use form as fungicides with other fungicides results in an enlargement of the fungicidal spectrum of action in many cases.
Die folgende Liste von Fungiziden, mit denen die erfindungsgemäßen Verbindungen gemeinsam angewendet werden können, soll die Kombinationsmöglichkeiten erläutern, nicht aber einschränken:The following list of fungicides with which the compounds according to the invention can be used together is intended to explain, but not to limit, the possible combinations:
• Schwefel, Dithiocarbamate und deren Derivate, wie Ferridimethyldithiocarbamat, Zinkdimethyldithiocarbamat, Zinkethylenbisdithiocarbamat, Manganethylenbis- dithiocarbamat, Mangan-Zink-ethylendiamin-bis-dithiocarbamat, Tetramethylthiu- ramdisulfide, Ammoniak-Komplex von Zink-(N,N-ethylen-bis-dithiocarbamat), Ammoniak-Komplex von Zink-(N,N'-propylen-bis-dithiocarbamat), Zink-(N,N'- propylen-bis-dithiocarbamat), N,N'-Polypropylen-bis-(thiocarbamoyl)disulfid; • Nitroderivate, wie Dinitro-(1-methylheptyl)-phenylcrotonat, 2-sec-Butyl-4,6- dinitrophenyl-3,3-dimethylacrylat, 2-sec-Butyl-4,6-dinitrophenyl- isopropylcarbonat, 5-Nitro-isophthalsäure-di-isopropylester;• Sulfur, dithiocarbamates and their derivatives, such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, manganese ethylene bisdithiocarbamate, manganese-zinc-ethylenediamine-bis-dithiocarbamate, tetramethylthi-ammonium-bis-dithiocarbamate, tetramethyl-ammonia-bis-dithiocarbamate, , Ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate), zinc (N, N'-propylene-bis-dithiocarbamate), N, N'-polypropylene-bis- (thiocarbamoyl) disulfide; Nitroderivate, such as dinitro- (1-methylheptyl) phenylcrotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenyl-isopropyl carbonate, 5-nitro- isophthalate di-isopropyl;
• heterocyclische Substanzen, wie 2-Heptadecyl-2-imidazolin-acetat, 2,4-Dichlor-6- (o-chloranilino)-s-triazin, O,O-Diethyl-phthalimidophosphonothioat, 5-Amino-1- [bis-(dimethylamino)-phosphinyl]-3-phenyl-1 ,2,4- triazol, 2,3-Dicyano-1 ,4- dithioanthrachinon, 2-Thio-1 ,3-dithiolo[4,5-b]chinoxalin, 1-(Butylcarbamoyl)-2- benzimidazol-carbaminsäuremethylester, 2-Methoxycarbonylamino- benzimidazol, 2-(Furyl-(2))-benzimidazol, 2-(Thiazolyl-(4))-benzimidazoI, N- (1 ,1 ,2,2-Tetrachlorethylthio)-tetrahydrophthalimid, N-Trichlormethylthio- tetrahydrophthalimid, N-Trichlormethylthio-phthalimid,Heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, O, O-diethyl-phthalimidophosphonothioate, 5-amino-1- [bis- (dimethylamino) phosphinyl] -3-phenyl-1, 2,4-triazole, 2,3-dicyano-1, 4-dithioanthraquinone, 2-thio-1, 3-dithiolo [4,5-b] quinoxaline, 1 - (Butylcarbamoyl) -2- benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benzimidazole, 2- (furyl- (2)) -benzimidazole, 2- (thiazolyl- (4)) - benzimidazoI, N- (1, 1, 2, 2-tetrachloroethylthio) tetrahydrophthalimide, N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthio-phthalimide,
• N-Dichlorfluormethylthio-N',N'-dimethyl-N-phenyl-schwefelsäure- diamid, 5- Ethoxy-3-trichlormethyl-1,2,3-thiadiazol, 2-Rhodanmethylthiobenzthiazol, 1,4- Dichlor-2,5-dimethoxybenzol, 4-(2-Chlorphenylhydrazono)-3-methyI-5-isoxazolon, Pyridin-2-thio-1-oxid, 8-Hydroxychinolin bzw. dessen Kupfersalz, 2,3-DihydrÖ-5- carboxanilido-6-methyl-1 ,4-oxathiin, 2,3-Dihydro-5-carboxanilido-6-methyl-1 ,4- oxathiin-4,4-dioxid, 2-Methyl-5,6-dihydro-4H-pyran-3-carbonsäure-anilid, 2- Methyl-furan-3-carbonsäureanilid, 2,5-Dimethyl-furan-3-carbonsäureanilid, 2,4,5- Trimethyl-furan-3-carbonsäureanilid, 2,5-Dimethyl-furan-3- carbonsäurecyclohexylamid, N-Cyclohexyl-N-methoxy-2,5-dimethyl-furan-3- carbonsäureamid, 2-Methyl-benzoesäure-aniIid, 2-l.od-benzoesäure-ani|id,.N: Formyl-N-morpholin-2,2,2-trichlorethylacetal, Piperazin-1 ,4-diylbis-1- (2,2,2-trichlorethyl)-formamid, 1-(3,4-Dichloranilino)-1-formylamino-2,2,2- trichlorethan, 2,6-Dimethyl-N-tridecyl-morpholin bzw. dessen Salze, 2,6-DimethyI- N-cyclododecyl-morpholin bzw. dessen Salze, N-[3-(p-tert.-Butylphenyl)-2- methyIpropyl]-cis-2,6-dimethyl-morpholin, N-[3-(p-tert.-Butylphenyl)-• N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-rhodanmethylthiobenzothiazole, 1,4-dichloro-2,5 -dimethoxybenzene, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thio-1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl -1,4-oxathiin, 2,3-dihydro-5-carboxanilido-6-methyl-1, 4-oxathiin-4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxylic acid -anilide, 2-methyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,4,5-trimethyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide , N-Cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxamide, 2-methylbenzoic acid analyte, 2-l . od-benzoic acid ani | id, .N : Formyl-N-morpholine-2,2,2-trichloroethyl acetal, piperazine-1,4-diylbis-1- (2,2,2-trichloroethyl) -formamide, 1- (3,4-dichloroanilino) -1-formylamino- 2,2,2-trichloroethane, 2,6-dimethyl-N-tridecyl-morpholine or its salts, 2,6-dimethyl-N-cyclododecyl-morpholine or its salts, N- [3- (p-tert. -Butylphenyl) -2-methylpropyl] -cis-2,6-dimethyl-morpholine, N- [3- (p-tert-butylphenyl) -
2-methylpropyl]-piperidin, 1-[2-(2,4-Dichlorphenyl)-4-ethyl- 1 ,3-dioxolan-2-yl-ethyl]-1 H-1 ,2,4-triazol, 1-[2-(2,4-Dichlorphenyl)-4-n-propyl-1 ,3- dioxolan-2-yl-ethyl]-1 H-1 ,2,4-triazol, N-(n-Propyl)-N-(2,4,6-trichlorphenoxyethyl)- N'-imidazol-yl-harnstoff, 1 -(4-Chlorphenoxy)-3,3-dimethyl-1 -(1 H-1 ,2,4-triazol-1 - yl)-2-butanon, 1-(4-Chlorphenoxy)-3,3-dimethyl-1-(1H-2-methylpropyl] piperidine, 1- [2- (2,4-dichlorophenyl) -4-ethyl-1, 3-dioxolan-2-yl-ethyl] -1 H-1, 2,4-triazole, 1- [2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl-ethyl] -1 H-1, 2,4-triazole, N- (n-propyl) -N - (2,4,6-trichlorophenoxyethyl) - N'-imidazol-ylurea, 1 - (4-chlorophenoxy) -3,3-dimethyl-1 - (1 H-1, 2,4-triazol-1 - yl) -2-butanone, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-
1,2,4-triazol-1-yl)-2-butanol, (2RS,3RS)-1-[3-(2-Chlorphenyl)-2-(4-fluorphenyl)- oxiran-2-ylmethyl]-1 H-1 ,2,4-triazol, -(2-Chlorphenyl)- -(4-chlorphenyl)-5- pyrimidin-methanol, 5-Butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidin, Bis- (p-chlorphenyl)-3-pyridinmethanol, 1 ,2-Bis-(3-ethoxycarbonyl-2- thioureido)-benzol, 1 ,2-Bis-(3-methoxycarbonyl-2-thioureido)-benzol,1,2,4-triazol-1-yl) -2-butanol, (2RS, 3RS) -1- [3- (2-chlorophenyl) -2- (4-fluorophenyl) oxiran-2-ylmethyl] -1 H-1, 2,4-triazole, - (2-chlorophenyl) - - (4-chlorophenyl) -5-pyrimidine-methanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis- (p-chlorophenyl) -3-pyridine-methanol, 1,2-bis (3-ethoxycarbonyl-2-thioureido) benzene, 1,2-bis (3-methoxycarbonyl-2-thioureido) benzene,
• Strobilurine wie Methyl-E-methoxyimino-[ -(o-tolyloxy)-o-tolyl]acetat, Methyl-E-2- {2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylat, Methyl-E- methoxyimino-[ -(2-phenoxyphenyl)]-acetamid, Methyl-E-methoxyimino-[σ-(2,5- dimethylphenoxy)-o-tolyI]-acetamid, • Anilinopyrimidine wie N-(4,6-Dimethylpyrimidin-2-yl)-anilin, N-[4-MethyI-6-(1- propinyl)-pyrimidin-2-yl]-anilin, N-[4-Methyl-6-cyclopropyl-pyrimidin-2-yl]-anilin,Strobilurins such as methyl-E-methoxyimino- [- (o-tolyloxy) -o-tolyl] acetate, methyl-E-2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate, methyl-E-methoxyimino- [- (2-phenoxyphenyl)] - acetamide, methyl-E-methoxyimino- [σ- (2,5-dimethylphenoxy) -o-tolyI] -acetamide, • anilinopyrimidines such as N - (4,6-Dimethylpyrimidin-2-yl) aniline, N- [4-methyl-6- (1-propynyl) pyrimidin-2-yl] aniline, N- [4-methyl-6-cyclopropyl- pyrimidin-2-yl] aniline,
• Phenylpyrrole wie 4-(2,2-Difluor-1 ,3-benzodioxoI-4-yl)-pyrrol-3-carbonitril,Phenylpyrroles such as 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyrrole-3-carbonitrile,
• Zimtsäureamide wie 3-(4-Chlorphenyl)-3-(3,4-dimethoxyphenyl)- acrylsäuremorpholid, • sowie verschiedene Fungizide, wie Dodecylguanidinacetat,Cinnamic acid amides such as 3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) acrylic morpholide, and various fungicides such as dodecylguanidine acetate,
3-[3-(3,5-Dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]-glutarimid, Hexachlorbenzol, DL-Methyl-N-(2,6-dimethyl-phenyl)-N-furoyl(2)-alaninat, DL-N-(2,6-Dimethyl- phenyl)-N-(2'-methoxyacetyl)-aIanin-methyl- ester, N-(2,6-Dimethylphenyl)-N- chloracetyl-D,L-2-aminobutyrolacton, DL-N-(2,6-Dimethylphenyl)rN- . (phenylacetyl)-alaninmethylester, 5-Methyl-5-vinyl-3-(3,5-dichlorphenyl)-2,4- dioxo-1 ,3-oxazolidin, 3-[3,5-Dichlorphenyl(-5-methyl-5-methoxymethyl]-1 ,3- oxazolidin- 2,4-dion, 3-(3,5-Dichlorphenyl)-1 -isopropylcarbamoylhydantoin, N-(3,5-Dichlorphenyl)-1 ,2-dimethylcyclopropan-1 ,2-dicarbonsäureimid, 2-Cyano- [N-(ethylaminocarbonyl)-2-methoximino]-acetamid, 1 -[2-(2,4-Dichlorphenyl)- pentyl]-1 H-1 ,2,4-triazol, 2,4-Difluor- -(1 H-1 ,2,4-triazolyl-1 -methyl)- benzhydrylalkohol, N-(3-Chlor-2,6-dinitro-4-trifluormethyl-phenyl)-5-trifluormethyl- 3-chlor-2-aminopyridin, 1-((bis-(4-Fluorphenyl)-methylsiIyl)-methyl)-1 H-1 ,2,4- triazol. Herstellungsbeispiele:3- [3- (3,5-Dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene, DL-methyl-N- (2,6-dimethyl-phenyl) -N-furoyl (2) alaninate , DL-N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) -alanine methyl ester, N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L-2- aminobutyrolactone, DL-N- (2,6-dimethylphenyl) rN-. (phenylacetyl) alanine methyl ester, 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1, 3-oxazolidine, 3- [3,5-dichlorophenyl (-5-methyl- 5-methoxymethyl] -1, 3-oxazolidine-2,4-dione, 3- (3,5-dichlorophenyl) -1 -isopropylcarbamoylhydantoin, N- (3,5-dichlorophenyl) -1, 2-dimethylcyclopropane-1,2 -dicarboximide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoximino] acetamide, 1 - [2- (2,4-dichlorophenyl) pentyl] -1 H-1, 2,4-triazole, 2, 4-difluoro- - (1 H-1, 2,4-triazolyl-1-methyl) - benzhydryl alcohol, N- (3-chloro-2,6-dinitro-4-trifluoromethyl-phenyl) -5-trifluoromethyl-3- chloro-2-aminopyridine, 1 - ((bis- (4-fluorophenyl) methylsilyl) methyl) -1 H-1, 2,4-triazole. Preparation Examples:
Beispiel 1 : 3-Trifluormethyl-picolinsäure-(ortho-cyclohexyl)-anilid:Example 1: 3-trifluoromethyl-picolinic acid (ortho-cyclohexyl) anilide:
1.1 3-Trifluormethylpyridin-2-carbonsäuremethylester:1.1 3-Trifluoromethylpyridine-2-carboxylic acid methyl ester:
66,8 g (0,4 mol) Pyridin-2,3-dicarbonsäure wurden in einem 0,5 I Autoklaven vorgelegt. Anschließend kondensierte man 120 g (6 mol) wasserfreien Fluorwasserstoff ein und presste 138,4 g (1,28 mol) Schwefeltetrafluorid auf. Man rührte 24 h bei 60 °C. Nach Entspannen gab man 150 ml Methanol in den Autoklaven und rührte anschließend 3 h bei 80°C unter Eigendruck. Nach Entspannen gab man den Autoklaveninhalt auf 1000 g Eiswasser, stellte mit 40 gew.-%iger wäss- riger Kaliumhydroxid-Lösung alkalisch, wusch 3 mal mit 350 ml Methylenchlorid, trennte die Methylenchloridphase ab, wusch einmal mit 300 ml Wasser und trocknete anschließend die organische Phase mit Magnesiumsulfat. Nach Abdes- tillieren des Lösungsmittels im Vakuum erhielt man einen Rückstand, der im Vakuum über eine 15 cm-Vigreuxkolonne destilliert wurde. Man erhielt 61 ,9 g der Titelverbindung als eine Fraktion bei 98-99°C (10 mbar) mit einer GC-Reinheit von 88,7%.66.8 g (0.4 mol) of pyridine-2,3-dicarboxylic acid were placed in a 0.5 l autoclave. 120 g (6 mol) of anhydrous hydrogen fluoride were then condensed in and 138.4 g (1.28 mol) of sulfur tetrafluoride were injected. The mixture was stirred at 60 ° C. for 24 h. After releasing the pressure, 150 ml of methanol were added to the autoclave and the mixture was then stirred for 3 hours at 80 ° C. under autogenous pressure. After the pressure had been released, the contents of the autoclave were poured into 1000 g of ice water, made alkaline with 40% strength by weight aqueous potassium hydroxide solution, washed 3 times with 350 ml of methylene chloride, the methylene chloride phase was separated off, washed once with 300 ml of water and then dried organic phase with magnesium sulfate. After distilling off the solvent in vacuo, a residue was obtained which was distilled in vacuo over a 15 cm Vigreux column. 61.9 g of the title compound were obtained as a fraction at 98-99 ° C. (10 mbar) with a GC purity of 88.7%.
1H-NMR (DMSO-d6): 3,05 ppm (s, 3H, OMe); 7,85 ppm (m, 1H , Pyridin-H); 8,40 ppm (d, 1H, Pyridin-H); 8,95 ppm (d, 1H, Pyridin-H).1H NMR (DMSO-d 6 ): 3.05 ppm (s, 3H, OMe); 7.85 ppm (m, 1H, pyridine-H); 8.40 ppm (d, 1H, pyridine-H); 8.95 ppm (d, 1H, pyridine-H).
1.2 3-Trifluormethylpyridin-2-carbonsäure Kaliumsalz:1.2 3-trifluoromethylpyridine-2-carboxylic acid potassium salt:
20 g (0,086 mol) 88,7%iger 3-Trifluormethylpyridin-2-carbonsäuremethylester und 300 ml 20 gew.-%ige wässrige Kaliumhydroxid-Lösung wurden 6 h zum-20 g (0.086 mol) of 88.7% 3-trifluoromethylpyridine-2-carboxylic acid methyl ester and 300 ml of 20% by weight aqueous potassium hydroxide solution were
Rückfluss erhitzt. Anschließend stellte man mit wässriger Salzsäure auf pH=5 und engte zur Trockene ein. Der Rückstand wurde zweimal mit 400 ml Methanol ausgekocht. Die Methanol extrakte wurde gesammelt und im Vakuum zur Trockne eingeengt. Auf diese Weise erhielt man 20,2 g der Titelverbindung als Kali- umsalz. H-NMR (DMSO-d6): 7,3 ppm (m, 1H , Pyridin-H); 7,95 ppm (d, 1H, Pyridin-H);Reflux heated. Then it was adjusted to pH = 5 with aqueous hydrochloric acid and concentrated to dryness. The residue was boiled twice with 400 ml of methanol. The methanol extracts were collected and evaporated to dryness in vacuo. In this way, 20.2 g of the title compound were obtained as the potassium salt. H NMR (DMSO-d 6 ): 7.3 ppm (m, 1H, pyridine-H); 7.95 ppm (d, 1H, pyridine-H);
8,6 ppm (d, 1H, Pyridin-H).8.6 ppm (d, 1H, pyridine-H).
1.3 3-Trifluormethyl-picolinsäure-(ortho-cyclohexyl)-anilid: In 20 ml Dichlormethan wurden 600 mg ortho-Cyclohexylanilin und 1 ,04 g1.3 3-Trifluoromethyl-picolinic acid (ortho-cyclohexyl) anilide: 600 mg of ortho-cyclohexylaniline and 1.04 g were added to 20 ml of dichloromethane
Triethylamin gelöst. Man gab 0,72 g 3-Trifluormethylpicolinsäurechlorid zu und rührte 14 h bei Raumtemperatur. Anschließend wurde die Reaktionsmischung je einmal mit wässrigem Natriumhydrogencarbonat und verdünnter Salzsäure und zweimal mit Wasser gewaschen. Die organische Phase wurde über Natriumsulfat getrocknet und im Vakuum eingeengt. Nach chromatographischer Reinigung des Rückstandes an Kieselgel mit einer Mischung aus Cyclohexan und Methyl-tert- butylether erhält man 740 mg der Zielverbindung mit einem Festpunkt von 111- 116°C.Triethylamine dissolved. 0.72 g of 3-trifluoromethylpicolinoyl chloride was added and the mixture was stirred at room temperature for 14 h. The reaction mixture was then washed once each with aqueous sodium hydrogen carbonate and dilute hydrochloric acid and twice with water. The organic phase was dried over sodium sulfate and concentrated in vacuo. After chromatographic cleaning of the Residue on silica gel with a mixture of cyclohexane and methyl tert-butyl ether gives 740 mg of the target compound with a fixed point of 111-116 ° C.
Die Verbindungen der Beispiele 2 bis 22 (Verbindungen der Formel I') wurden in analoger Weise hergestellt. Ihre physikochemischen Daten sind in Tabelle 7 zusammengestellt:The compounds of Examples 2 to 22 (compounds of the formula I ') were prepared in an analogous manner. Your physicochemical data are summarized in Table 7:
Tabelle 7:Table 7:
Figure imgf000037_0001
Figure imgf000037_0001
Figure imgf000037_0002
Figure imgf000038_0001
Figure imgf000037_0002
Figure imgf000038_0001
Anwendungsbeispiele:Application examples:
Die Wirkstoffe wurden als Stammlösung aufbereitet mit 0,25 Gew.-% Wirkstoff in Ace- ton oder Dimethylsulfoxid (DMSO). Dieser Lösung wurde 1 Gew.-% Emulgator Unipe- rol® EL (Netzmittel mit Emulgier- und Dispergierwirkung auf der Basis ethoxylierter Alkylphenole) zugesetzt und entsprechend der gewünschten Konzentration mit Wasser verdünnt.The active ingredients were prepared as a stock solution with 0.25% by weight of active ingredient in acetone or dimethyl sulfoxide (DMSO). 1% by weight of the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) was added to this solution and diluted with water to the desired concentration.
Wirksamkeit gegen Mehltau an Gurkenblättern verursacht durch Sphaerotheca fuliginea bei protektiver AnwendungEfficacy against mildew on cucumber leaves caused by Sphaerotheca fuliginea when used protectively
Blätter von in Töpfen gewachsenen Gurkenkeimlingen der Sorte "Chinesische. Schlan- ge" wurden im Keimblattstadium mit wässriger Suspension in der unten angegebenen Wirkstoffkonzentration bis zur Tropfnässe besprüht. 20 h nach dem Antrocknen des Spritzbelags wurden die Pflanzen mit einer wässrigen Sporensuspension des Gurkenmehltaus (Sphaerotheca fuliginea) inokuliert. Danach wurden die Versuchspflanzen im Gewächshaus bei Temperaturen zwischen 20 und 24 °C und 60 bis 80 % relativer Luft- feuchtigkeit für 7 Tage kultiviert. Danach wurde das Ausmaß der Mehltauentwicklung visuell in %-Befall der Keimblattfläche ermittelt. Die Ergebnisse sind in Tabelle 8 zusammengestellt.In the cotyledon stage, leaves of cucumber seedlings of the "Chinese. Snake" variety, grown in pots, were sprayed to runoff point with an aqueous suspension in the active compound concentration given below. 20 h after the spray coating had dried on, the plants were inoculated with an aqueous spore suspension of cucumber mildew (Sphaerotheca fuliginea). The test plants were then cultivated in a greenhouse at temperatures between 20 and 24 ° C. and 60 to 80% relative atmospheric humidity for 7 days. The extent of mildew development was then determined visually in% of the cotyledon area. The results are summarized in Table 8.
Tabelle 8:Table 8:
Figure imgf000038_0002
Figure imgf000039_0001
Figure imgf000038_0002
Figure imgf000039_0001
Protektive Wirksamkeit gegen Puccinia recondita an Weizen (Weizenbraunrost)Protective activity against Puccinia recondita on wheat (wheat brown rust)
Blätter von in Töpfen gewachsenen Weizensämlingen der Sorte "Kanzler" wurden mit einer wässrigen Suspension in der unten angegebenen Wirkstoffkonzentration bis zur Tropfnässe bestäubt. Am nächsten Tag wurden die behandelten Pflanzen mit Sporen des Weizenbraunrostes (Puccinia recondita) bestäubt. Anschließend wurden die Pflanzen für 24 Stunden in eine Kammer mit hoher Luftfeuchtigkeit (90 bis 95 %) und 20 bis 22 °C gestellt. Während dieser Zeit keimten die Sporen aus und die Keimschläuche drangen in das Blattgewebe ein. Am folgenden Tag wurden die Versuchspflanzen ins Gewächshaus zurückgestellt und bei Temperaturen zwischen 20 und 22 °C und 65 bis 70 % relativer Luftfeuchtigkeit für weitere 7 Tage kultiviert. Danach wurde das Ausmaß der Rostpilzentwicklung auf den Blättern visuell ermittelt. Die Ergebnisse sind in Tabel- le 9 zusammengestellt.Leaves of potted wheat seedlings of the "Kanzler" variety were dusted to runoff point with an aqueous suspension in the concentration of active ingredient specified below. The next day, the treated plants were dusted with spores of the wheat brown rust (Puccinia recondita). The plants were then placed in a chamber with high atmospheric humidity (90 to 95%) and 20 to 22 ° C. for 24 hours. During this time, the spores germinated and the germ tubes penetrated the leaf tissue. The following day, the test plants were returned to the greenhouse and cultivated at temperatures between 20 and 22 ° C. and 65 to 70% relative atmospheric humidity for a further 7 days. The extent of the rust fungus development on the leaves was then determined visually. The results are summarized in Table 9.
Tabelle 9:Table 9:
Figure imgf000039_0002
Figure imgf000039_0002

Claims

Patentansprüche claims
1. 3-TrifluormethyIpicolinsäureanilide der allgemeinen Formel I,1. 3-trifluoromethylpicolinic acid anilides of the general formula I,
Figure imgf000040_0001
Figure imgf000040_0001
worin n für 0, 1 , 2, 3 oder 4 steht und die Substituenten die folgende Bedeutung haben:where n is 0, 1, 2, 3 or 4 and the substituents have the following meaning:
X O, S oder direkte Bindung;X O, S or direct bond;
W O oder S; R\ R2, R3 unabhängig voneinander Wasserstoff, Halogen, Nitro, CN, d-C4- Alkyl, C3-C6-Cycloalkyl, C2-C4-Alkenyl, C2-C4-Alkinyl, C C4-Alkoxy, wobei die Wasserstoffatome in den 4 zuletzt genannten Gruppen teilweise oder vollständig durch Halogen substituiert sein können;WO or S; R \ R 2 , R 3 independently of one another are hydrogen, halogen, nitro, CN, dC 4 -alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, CC 4 -alkoxy , where the hydrogen atoms in the last 4 groups mentioned can be partially or completely substituted by halogen;
R4 Wasserstoff, OH, CrC4-Alkyl, C3-C6-Cycloalkyl, C C4-Alkoxy, wobei die Wasserstoffatome in den 3 zuletzt genannten Gruppen teilweise oder vollständig durch Halogen substituiert sein können; unsubstituiertes C4-C12-Alkyl, C3-C12-Cycloalkyl, C3-C12-Alkenyl, C5- C12-Cycloalkenyl, C3-C12-Alkinyl, C3-C12-Cycloalkyl-d-C4-alkyl, wobei die 5 letztgenannten Gruppen jeweils 1 , 2 oder 3 Substituenten R9 aufweisen können, und wobei die Wasserstoffatome in den 5 letztgenannten Gruppen teilweise oder vollständig durch Halogen substituiert sein können; d-C12-Halogenalkyl, C C12-Alkyl, das 1 , 2 oder 3 Substituenten R11 aufweist, eine Gruppe -C(R10)=NOR8, eine Gruppe -C(O)NR13R14; Phenyl, Phenyl-C C6-alkyl, Phenyl-C2-C6-alkenyl, Phenyl-C2-C6- alkinyl, Phenyloxy-C C6-alkyl, Phenyloxy-C2-C6-älkenyl, Phenyloxy- C2-C6-alkinyl, wobei der Alkyl-, Alkenyl- und der Alkinyl-Teil in den 6 zuletzt genannten Gruppen 1 , 2, 3 oder 4 Substituenten R11 aufweisen kann und der Phenylring in den 7 zuletzt genannten Gruppen 1, 2, 3 oder 4 Reste R7 tragen kann; die für R1 genannten, von Wasserstoff verschiedenen Bedeutungen; R7 d-C4-Alkyl, C3-C6- Cycloalkyl, C C4-Alkoxy, C2-C4-Alkenyl, C2-C4-R 4 is hydrogen, OH, C r C 4 alkyl, C 3 -C 6 cycloalkyl, CC 4 alkoxy, where the hydrogen atoms in the last 3 groups mentioned can be partially or completely substituted by halogen; unsubstituted C 4 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 3 -C 12 alkenyl, C 5 - C 12 cycloalkenyl, C 3 -C 12 alkynyl, C 3 -C 12 cycloalkyl-dC 4 -alkyl, where the latter 5 groups can each have 1, 2 or 3 substituents R 9 , and where the hydrogen atoms in the 5 latter groups can be partially or completely substituted by halogen; dC 12 haloalkyl, CC 12 alkyl which has 1, 2 or 3 substituents R 11 , a group -C (R 10 ) = NOR 8 , a group -C (O) NR 13 R 14 ; Phenyl, phenyl-C 6 alkyl, phenyl C 2 -C 6 -alkenyl, phenyl C 2 -C 6 -alkynyl, phenyloxy-C 6 -alkyl, phenyloxy-C 2 -C 6 -alkenyl, phenyloxy- C 2 -C 6 alkynyl, where the alkyl, alkenyl and alkynyl part in the 6 last-mentioned groups can have 1, 2, 3 or 4 substituents R 11 and the phenyl ring in the 7 last-mentioned groups 1, 2 , Can carry 3 or 4 residues R 7 ; the meanings given for R 1 , other than hydrogen; R 7 dC 4 alkyl, C 3 -C 6 cycloalkyl, CC 4 alkoxy, C 2 -C 4 alkenyl, C 2 -C 4 -
Alkenyloxy, C2-C4-Alkinyl, C2-C4-Alkinyloxy, wobei die Wasserstoffatome in diesen 7 Gruppen teilweise oder vollständig durch Halogen substituiert sein können, OH, Halogen, Nitro, CN, C C -Alkylthio, C C4-Alkylsulfonyl, -C(O)R12, NR13R14, -C(O)NR13R14, -C(S)NR13R14,Alkenyloxy, C 2 -C 4 -alkynyl, C 2 -C 4 -alkynyloxy, where the hydrogen atoms in these 7 groups can be partially or completely substituted by halogen, OH, halogen, nitro, CN, CC -alkylthio, CC 4 -alkylsulfonyl , -C (O) R 12 , NR 13 R 14 , -C (O) NR 13 R 14 , -C (S) NR 13 R 14 ,
-C(R10)=NOR8, Phenyl, das 1 , 2, 3 oder 4 der unter R6 genannten Gruppen aufweisen kann, Phenoxy, das 1 , 2, 3 oder 4 der unter R6 genannten Gruppen aufweisen kann, d-C6-Alkyl-Phenyl, wobei die Wasserstoffatome des Alkylteils teilweise oder vollständig durch Ha- logen substituiert sein können und der Phenylring 1 , 2, 3 oder 4 der unter R6 genannten Gruppen aufweisen kann, wobei zwei an benachbarte Kohlenstoffatome gebundene Reste R7 auch für CH=CH-CH=CH oder eine Alkylenkette mit 3 bis 5 Gliedern stehen können, worin 1 oder 2 nicht benachbarte CH2-Gruppen auch durch Sauerstoff oder Schwefel ersetzt sein können und worin ein-C (R 10 ) = NOR 8 , phenyl which may have 1, 2, 3 or 4 of the groups mentioned under R 6 , phenoxy which may have 1, 2, 3 or 4 of the groups mentioned under R 6 , dC 6 -Alkyl-phenyl, where the hydrogen atoms of the alkyl part can be partially or completely substituted by halogen and the phenyl ring can have 1, 2, 3 or 4 of the groups mentioned under R 6 , with two radicals R 7 bonded to adjacent carbon atoms also for CH = CH-CH = CH or an alkylene chain having 3 to 5 links, in which 1 or 2 non-adjacent CH 2 groups can also be replaced by oxygen or sulfur and in which a
Teil oder alle Wasserstoffe durch Halogen ersetzt sein können; R8 C C4-Alkyl, C3-C6- Cycloalkyl, C2-C4-Alkenyl, C2-C4-Alkinyl, wobei diePart or all of the hydrogen can be replaced by halogen; R 8 CC 4 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, the
Wasserstoffatome in diesen 4 Gruppen teilweise oder vollständig, durch Halogen substituiert sein können, Phenyl oder Phenyl-C C6-alkyl, wobei Phenyl in den zwei letztgenannten Resten 1 , 2, 3 oder 4 der unter R6 genannten Gruppen aufweisen kann; R9 CrC -Alkyl, d-C8-Alkoxy, C2-C8-Alkenyloxy, C2-C8-Alkinyloxy, d-C4-Hydrogen atoms in these 4 groups can be partially or completely substituted by halogen, phenyl or phenyl-C 6 alkyl, where phenyl in the latter two radicals can have 1, 2, 3 or 4 of the groups mentioned under R 6 ; R 9 C r C alkyl, dC 8 alkoxy, C 2 -C 8 alkenyloxy, C 2 -C 8 alkynyloxy, dC 4 -
Alkoxy-d-C8-alkoxy, wobei die Wasserstoffatome in diesen Gruppen teilweise oder vollständig durch Halogen substituiert sein können;Alkoxy-dC 8 -alkoxy, where the hydrogen atoms in these groups can be partially or completely substituted by halogen;
R10 Wasserstoff, Halogen, d-C8-Alkoxy, C2-C8-Alkenyloxy, C2-C8-R 10 is hydrogen, halogen, dC 8 alkoxy, C 2 -C 8 alkenyloxy, C 2 -C 8 -
Alkinyloxy, C C -Alkoxy-Cι-C8-alkoxy, d-C12-Alkyl, C3-C1 - Cycloalkyl, C2-C12-Alkenyl, C5-C12-Cycloalkenyl, C3-C12-Cycloalkyl-d- C -alkyl, wobei die Wasserstoffatome in den 9 zuletzt genannten Gruppen teilweise oder vollständig durch Halogen substituiert sein können;Alkynyloxy, CC -alkoxy-C 8 -alkoxy, dC 12 -alkyl, C 3 -C 1 cycloalkyl, C 2 -C 12 alkenyl, C 5 -C 12 cycloalkenyl, C 3 -C 12 cycloalkyl- d- C -alkyl, where the hydrogen atoms in the last 9 groups mentioned can be partially or completely substituted by halogen;
Phenyl, das 1 , 2, 3 oder 4 der unter R7 genannten Gruppen aufweisen kann, R11 Halogen, d-C4-Alkyl, d-C8-Alkoxy, C C8-Alkoxy-d-C8-alkoxy, C2- C8-Alkenyloxy, C2-C8-Alkinyloxy, CrC4-Alkoxy-C C8-alkoxy, wobei die Wasserstoffatome in diesen Gruppen teilweise oder vollständig durch Halogen substituiert sein können; R12 Wasserstoff, OH, CrC4-Alkyl, C C4-Alkoxy, C2-C4-Alkenyl, C2-C4-Phenyl, which can have 1, 2, 3 or 4 of the groups mentioned under R 7 , R 11 is halogen, dC 4 -alkyl, dC 8 -alkoxy, CC 8 -alkoxy-dC 8 -alkoxy, C 2 - C 8 -alkenyloxy , C 2 -C 8 alkynyloxy, C r C 4 -alkoxy-C C 8 -alkoxy, where the hydrogen atoms in these groups can be partially or completely substituted by halogen; R 12 is hydrogen, OH, C r C 4 alkyl, CC 4 alkoxy, C 2 -C 4 alkenyl, C 2 -C 4 -
Alkinyl, C2-C4-Alkenyloxy, C2-C -Alkinyloxy, d-C4-Alkoxy-CrC4- alkoxy, wobei die Wasserstoffatome in den 7 zuletzt genannten Gruppen teilweise oder vollständig durch Halogen substituiert seϊn können; R13, R14 unabhängig voneinander Wasserstoff, C C4-AlkyI, C2-C4-Alkenyl, C2- C4-Alkinyl, wobei die Wasserstoffatome in diesen Gruppen teilweise oder vollständig durch Halogen substituiert sein können;Alkynyl, C 2 -C 4 -alkenoxy, C 2 -C -alkynyloxy, dC 4 -alkoxy-C r C 4 - alkoxy, the hydrogen atoms in the last 7 mentioned Groups can be partially or completely substituted by halogen; R 13, R 14 are independently hydrogen, CC -AlkyI 4, C 2 -C 4 alkenyl, C 2 - C 4 alkynyl, wherein the hydrogen atoms may be partially completely substituted in these groups or by halogen;
und die landwirtschaftlich brauchbaren Salze von I.and the agriculturally useful salts of I.
2. Anilide der allgemeinen Formel I nach Anspruch 1 , worin R1, R2 und R3 unab- hängig voneinander Wasserstoff, Halogen, C C4-Alkyl oder CrC -Halogenalkyl bedeuten.2. Anilides of the general formula I according to Claim 1, in which R 1 , R 2 and R 3 independently of one another are hydrogen, halogen, CC 4 alkyl or C r C haloalkyl.
3. Anilide der allgemeinen Formel l nach Anspruch 1 , worin R1, R2 und R3 jeweils für Wasserstoff stehen.3. Anilides of the general formula I according to claim 1, wherein R 1 , R 2 and R 3 each represent hydrogen.
4. Anilide der allgemeinen Formel I nach einem der vorhergehenden Ansprüche, worin R4 ausgewählt ist unter Wasserstoff, Methyl, OH oder Methoxy.4. Anilides of the general formula I according to any one of the preceding claims, wherein R 4 is selected from hydrogen, methyl, OH or methoxy.
5. Anilide der allgemeinen Formel I nach Anspruch 4, worin R4 für Wasserstoff steht.5. anilides of the general formula I according to claim 4, wherein R 4 is hydrogen.
6. Anilide der allgemeinen Formel l nach einem der vorhergehenden Ansprüche, worin R5 eine der folgenden Bedeutungen aufweist:6. Anilides of the general formula I according to one of the preceding claims, in which R 5 has one of the following meanings:
- unsubstituiertes C -C12-Alkyl, C3-C12-Cycloalkyl, C2-C12-Alkenyl, C5-C12-- Unsubstituted C -C 12 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 12 alkenyl, C 5 -C 12 -
Cycloalkenyl, C2-C12-Alkinyl, wobei die Wasserstoffatome in den 4 zuletzt genannten Gruppen teilweise oder vollständig durch Halogen substituiert sein können und die Wasserstoffatome in C3-C12-Cycloalkyl teilweise oder vollständig durch d-C4-Alkyl substituiert sein können, - C d2-Halogenalkyl, C C -Alkoxy-d-C -alkyl, d-d-Halogenalkoxy-d-d- alkyl;Cycloalkenyl, C 2 -C 12 alkynyl, where the hydrogen atoms in the last 4 groups mentioned can be partially or completely substituted by halogen and the hydrogen atoms in C 3 -C 12 cycloalkyl can be partially or completely substituted by dC 4 alkyl, - C d 2 haloalkyl, CC alkoxy-dC-alkyl, dd-haloalkoxy-dd-alkyl;
Phenyl, Phenyl-CrC6-alkyl, wobei der Phenylring mit 1 , 2, 3 oder 4 Resten R7 substituiert sein kann; oder -C(Cι-C4-Alkyl)=NO-R8, wobei die Wasserstoffatome der C C4-Alkylgruppe teilweise oder vollständig durch Halogen substituiert sein können.Phenyl, phenyl-C r C 6 -alkyl, where the phenyl ring can be substituted by 1, 2, 3 or 4 radicals R 7 ; or -C (-C-C 4 alkyl) = NO-R 8 , where the hydrogen atoms of the CC 4 alkyl group can be partially or completely substituted by halogen.
7. Anilide der allgemeinen Formel I nach einem der vorhergehenden Ansprüche, in denen R6 die folgenden Bedeutungen aufweist CrC4-Alkyl, C C4-Alkoxy, wobei diese Gruppen durch Halogen substituiert sein können, oder Halogen. 7. Anilides of the general formula I according to one of the preceding claims, in which R 6 has the following meanings C r C 4 alkyl, CC 4 alkoxy, where these groups can be substituted by halogen, or halogen.
8. Anilide der allgemeinen Formel I nach einem der vorhergehenden Ansprüche, in denen n = 0 ist.8. Anilides of the general formula I according to one of the preceding claims, in which n = 0.
9. Anilide der allgemeinen Formel I nach Anspruch 9, worin R1, R2 und R3 jeweils für Wasserstoff stehen und die Gruppe X-R5 in ortho- oder meta-Position zum Amidstickstoff gebunden ist.9. anilides of the general formula I according to claim 9, wherein R 1 , R 2 and R 3 each represent hydrogen and the group XR 5 is bonded in the ortho or meta position to the amide nitrogen.
10. Anilide der allgemeinen Formel I nach einem der vorhergehenden Ansprüche, in denen X eine direkte Bindung oder Sauerstoff bedeutet.10. Anilides of the general formula I according to one of the preceding claims, in which X denotes a direct bond or oxygen.
11. Anilide der allgemeinen Formel l nach Anspruch 10, in denen die Gruppe X für Sauerstoff oder eine direkte Bindung steht und R5 eine der folgenden Bedeutungen aufweist:11. Anilides of the general formula I according to claim 10, in which the group X represents oxygen or a direct bond and R 5 has one of the following meanings:
- unsubstituiertes C -C12-Alkyl, C3-C12-Cycloalkyl, C2-C12-Alkenyl, C5-C12-- Unsubstituted C -C 12 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 12 alkenyl, C 5 -C 12 -
Cycloalkenyl, C2-d2-Alkinyl, wobei die Wasserstoffatome in den 4 zuletzt genannten Gruppen teilweise oder vollständig durch Halogen substituiert sein können und die Wasserstoffatome in C3-C12-Cycloalkyl teilweise oder vollständig durch C C4-Alkyl substituiert sein können; - d-C12-Halogenalkyl, d-C4-Alkoxy-d-C4-alkyl, d-C4-Halogenalkoxy-d-C4- alkyl;Cycloalkenyl, C 2 -d 2 -alkynyl, where the hydrogen atoms in the last 4 groups mentioned can be partially or completely substituted by halogen and the hydrogen atoms in C 3 -C 12 -cycloalkyl can be partly or completely substituted by CC 4 -alkyl; dC 12 haloalkyl, dC 4 alkoxy-dC 4 alkyl, dC 4 haloalkoxy-dC 4 alkyl;
Phenyl, Phenyl-CrC6-alkyl, wobei der Phenylring mit 1, 2, 3 oder 4 Resten R7 substituiert sein kann; oder -C(C C4-Alkyl)=NO-R8, wobei die Wasserstoffatome der d-C -Alkylgruppe teilweise oder vollständig durch Halogen substituiert sein können.Phenyl, phenyl-CrC 6 -alkyl, where the phenyl ring can be substituted by 1, 2, 3 or 4 radicals R 7 ; or -C (CC 4 -alkyl) = NO-R 8 , where the hydrogen atoms of the dC -alkyl group can be partially or completely substituted by halogen.
12. Verwendung von 3-Trifluormethylpicolinsäureaniliden der allgemeinen Formel I und ihren landwirtschaftlich verträglichen Salzen gemäß einem der vorhergehenden Ansprüche zur Bekämpfung von Schadpilzen.12. Use of 3-trifluoromethylpicolinic anilides of the general formula I and their agriculturally acceptable salts according to one of the preceding claims for combating harmful fungi.
13. Fungizide Mittel, enthaltend eine fungizid wirksame Menge mindestens eines 3- Trifluormethylpicolinsäureanilids der allgemeinen Formel I oder eines landwirtschaftlich verträglichen Salzes von I gemäß einem der Ansprüche 1 bis 11.13. Fungicidal compositions comprising an fungicidally effective amount of at least one 3-trifluoromethylpicolinic acid anilide of the general formula I or an agriculturally acceptable salt of I according to any one of claims 1 to 11.
14. Verfahren zur Bekämpfung von Schadpilzen, dadurch gekennzeichnet, dass man die Schadpilze, deren Lebensraum oder die von ihnen freizuhaltenden Pflanzen, Flächen, Materialien oder Räume mit mindestens einer fungizid wirksamen Menge eines 3-Trifluormethylpicolinsäureanilids der allgemeinen Formel I oder eines landwirtschaftlich verträglichen Salzes von I gemäß einem der Ansprüche 1 bis 11 behandelt. 14. A method for combating harmful fungi, characterized in that the harmful fungi, their habitat or the plants, areas, materials or spaces to be kept free of them with at least one fungicidally effective amount of a 3-trifluoromethylpicolinic acid anilide of the general formula I or an agriculturally acceptable salt of I treated according to one of claims 1 to 11.
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