WO2005063710A1 - Anilides d'acide 3-trifluoromethylpicolinique et leur utilisation comme fongicides - Google Patents

Anilides d'acide 3-trifluoromethylpicolinique et leur utilisation comme fongicides 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)
English (en)
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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 EP04804216A priority Critical patent/EP1699763A1/fr
Priority to JP2006546061A priority patent/JP2007534652A/ja
Publication of WO2005063710A1 publication Critical patent/WO2005063710A1/fr

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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

L'invention concerne des anilides d'acide 3-trifluorométhylpicolinique de formule générale (I), dans laquelle X représente oxygène, soufre ou une liaison directe et W représente oxygène ou soufre, n vaut 0, 1, 2, 3 ou 4 et les substituants ont la signification indiquée dans les revendications. L'invention concerne également les sels de (I) utilisables dans l'agriculture, l'utilisation comme fongicides des anilides d'acide 3-trifluorométhylpicolinique de formule générale (I) et de leurs sels utilisables dans l'agriculture, ainsi que des agents phytosanitaires les contenant.
PCT/EP2004/014621 2003-12-23 2004-12-22 Anilides d'acide 3-trifluoromethylpicolinique et leur utilisation comme fongicides WO2005063710A1 (fr)

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JP2006546061A JP2007534652A (ja) 2003-12-23 2004-12-22 ３−トリフルオロメチルピコリン酸アニリドおよび殺菌剤としてのその使用

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WO2007017450A1 (fr) * 2005-08-05 2007-02-15 Basf Se Fongicides de n-[2-(haloalkoxy)phenyl]heteroarylcarboxamides
WO2007017231A1 (fr) * 2005-08-05 2007-02-15 Basf Aktiengesellschaft Utilisation d’arylanilides pour traiter des graines
WO2007017409A1 (fr) * 2005-08-05 2007-02-15 Basf Se Méthode pour contrôler les infections de légumineuses par la rouille
WO2007068376A1 (fr) * 2005-12-17 2007-06-21 Bayer Cropscience Ag Biphenylcarboxamides pour lutter contre les micro-organismes
US9011831B2 (en) 2004-09-30 2015-04-21 Advanced Cardiovascular Systems, Inc. Methacrylate copolymers for medical devices
US9538755B2 (en) 2004-08-12 2017-01-10 Syngenta Crop Protection, Llc Fungicidal compositions
CN109553578A (zh) * 2018-12-20 2019-04-02 西安近代化学研究所 一种联苯类化合物及制备方法和应用
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US11873309B2 (en) 2016-06-20 2024-01-16 Incyte Corporation Heterocyclic compounds as immunomodulators

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