EP1335903A1 - 2-aryl-5-trifluoromethylpyridine - Google Patents

2-aryl-5-trifluoromethylpyridine

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Publication number
EP1335903A1
EP1335903A1 EP01995651A EP01995651A EP1335903A1 EP 1335903 A1 EP1335903 A1 EP 1335903A1 EP 01995651 A EP01995651 A EP 01995651A EP 01995651 A EP01995651 A EP 01995651A EP 1335903 A1 EP1335903 A1 EP 1335903A1
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Prior art keywords
alkyl
alkoxy
phenyl
hydrogen
halogen
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EP01995651A
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German (de)
English (en)
Inventor
Michael Puhl
Andreas Gypser
Gerhard Hamprecht
Thorsten Volk
Peter Schäfer
Robert Reinhard
Ingo Sagasser
Cyrill Zagar
Matthias Witschel
Andreas Landes
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BASF SE
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BASF SE
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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
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • 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
    • C07D213/61—Halogen atoms or nitro radicals
    • 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
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • 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
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • C07D213/71—Sulfur atoms to which a second hetero atom is attached
    • 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
    • C07D213/72—Nitrogen atoms
    • C07D213/73—Unsubstituted amino or imino radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/04—Esters of boric acids

Definitions

  • the present invention relates to 2-aryl-5-trifluoromethylpyridines, their pyridine-N-oxides and their agriculturally useful salts and their use as herbicides, desiccants or defoliants.
  • Herbicidally active 2-aryl-5-trifluoromethylpyridines have been described variously in the prior art (see, for example, DE 4323916, WO 95/02580, WO 95/02590, WO 96/21645, WO 96/21646, WO 96/21647, WO 96/21645, WO 97/06143, WO 97/11059, WO 97/30059, WO 98/07700 and WO 99/06394).
  • the 2-aryl-5-trifluoromethylpyridines known from the prior art sometimes leave something to be desired in terms of their activity and / or selectivity towards harmful plants.
  • the present invention is therefore based on the object of providing new herbicides with which harmful plants can be controlled better than hitherto.
  • the new herbicides should advantageously have a high activity against harmful plants.
  • crop tolerance is desirable.
  • 2-aryl-5-trifluoromethylpyridines, their N-oxides and their salts suitable for agricultural purposes have a particularly high herbicidal activity if they have an amino group or a methyl group in the 4-position of the pyridine ring have the 3-position carries a halogen atom and the 6-position is unsubstituted.
  • the present invention relates to 2-aryl-5-trifluoromethylpyridines of the general formula I.
  • X is a chemical bond, a methylene, 1,2-ethylene, propane-l, 3-diyl, ethene-1, 2-diyl or ethyne-1, 2-diyl chain or one via the hetero atom oxyiriethylene or thiamethylene chain bound to the phenyl ring, it being possible for all the chains to be unsubstituted or to carry one or two substituents, each selected from the group consisting of cyano, carboxy, halogen, C 1 -C 4 -alkyl, Cx - -Halogenalkyl, -CC 4 alkoxy, (-C -alkoxy) carbonyl, di- (-CC alkyl) amino and phenyl;
  • R 3 is hydrogen or halogen
  • R 4 halogen, cyano, OH, C ⁇ -C 4 alkoxy or -CC-alkoxycarbonyl- C C-C alkoxy;
  • R 5 hydrogen, nitro, cyano, halogen, halosulfonyl, N 3 , -0-YR 7 , -O-CO-YR 7 , -N (YR 7 ) (ZR 8 ), -N (YR 7 ) -S0 2 - ZR 8 ,
  • R 6 is hydrogen or
  • R 4 and XR 5 or XR 5 and R 6 are a 3- or 4-membered chain, the chain links of which, in addition to carbon, can have 1, 2 or 3 heteroatoms, selected from nitrogen, oxygen and sulfur atoms, which are unsubstituted or in turn have one , can carry two or three substituents, and the members of which can also comprise one or two non-adjacent carbonyl, thiocarbonyl or sulfonyl groups,
  • Y, Z independently of one another: a chemical bond, a methylene or ethylene group, which may be unsubstituted or carry one or two substituents, each selected from the group consisting of Carboxy, C ⁇ -C 4 -alkyl, C 4 haloalkyl, (C ⁇ -C 4 alkoxy) carbo- nyl, and phenyl;
  • R 7 , R 8 independently of one another: hydrogen, C 3 -C 8 cycloalkyl-C 4 -C 4 alkyl,
  • Heterocyclyl ring may be unsubstituted or may carry one, two, three or four substituents, each selected from the group consisting of cyano, nitro, amino, hydroxy, carboxy, halogen, C ⁇ -C 4 -alkyl, C 4 haloalkyl, C ⁇ -C 4 -alkoxy, C 4 haloalkoxy, C ⁇ -C 4 alkylthio, C ⁇ -C4-haloalkylthio, C ⁇ -C 4 alkylsulfonyl, C ⁇ -C4-haloalkylsulfonyl, (C ⁇ -C -alkyl) carbonyl , (-C-C 4 -haloalkyl) carbonyl, (-C-C 4 -alkyl) carbonyloxy, (-C-C 4 -haloalkyl) carbonyloxy, (C ⁇ -C 4 -alkoxy) carbonyl and di- (C 1 -C 4 alkyl)
  • R 9 is hydrogen, -CC 6 -alkyl, -C-alkoxycarbonyl -CC-C 4 -alkoxy, C 4 -C 8 cycloalkyl-C 1 -C -alkyl, C ⁇ -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 3 -C 8 cycloalkyl, phenyl or phenyl -CC 4 -alkyl ;
  • R 12, R 13 independently of one another are hydrogen, C 6 -alkyl, C 6 haloalkyl, C ⁇ -C 4 -alcohol xy-C ⁇ -C 4 alkyl, C 2 -C 6 alkenyl, C 2 - C 6 -haloalkenyl, C 2 -C 6 -alkynyl, C 2 -C 6 -haloalkynyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkyl-C 1 -C 4 -alkyl, phenyl, Phenyl-C 1 -C 4 -alkyl, 3- to 7-membered heterocyclyl or heterocyclyl-C 1 -C 4 -alkyl, where each cycloalkyl and each heterocyclyl ring can contain a carbonyl or thiocarbonyl ring member, and wherein each Cycloalkyl, the phenyl and each heterocyclyl
  • R 14 is hydrogen, C ⁇ -C 6 -alkyl, C ⁇ -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -haloalkenyl, CC 6 -alkynyl, CC 6 -haloalkynyl, C 3 -C 8 - Cycloalkyl, -CC 4 alkoxycarbonyl -CC 4 -alkyl, phenyl or phenyl -CC 4 -alkyl;
  • the invention also relates to: the use of compounds I and their salts as
  • Plants, herbicidal agents and agents for the desiccation and / or defoliation of plants which contain the compounds I and / or their salts as active substances, intermediates for the preparation of the compounds I Process for the preparation of herbicidal agents and agents for the desiccation and / or defoliation of Plants using the compounds I, and
  • the compounds of the formula I can form geometric isomers in the substituents, for example E / z isomers.
  • the invention relates to both the pure isomers and their mixtures.
  • the Compounds of the formula I can also have one or more centers of chirality in the substituents and are then present as enantiomer or diastereomer mixtures.
  • the invention relates both to the pure enantiomers or diastereomers and to their mixtures.
  • 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 herbicidal 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, as well as the ammonium ion, if desired one to four C ⁇ -C -Alkyl- and / or a phenyl or benzyl substituent can wear, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, further phosphonium ions, sulfonium ions, preferably tri (-C 4 alkyl) sulfonium and sulfoxonium ions, preferably tri (C ⁇ -C)
  • 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, and the anions of C 1 -C 4 -alkanoic acids, preferably Formate, acetate, 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.
  • halogenated Substituents preferably carry one, two, three, four or five identical or different halogen atoms. Halogen is fluorine, chlorine, bromine or iodine.
  • -C-C 4 alkyl for: CH 3 , C 2 H 5 , n-propyl, CH (CH 3 ) 2 , n-butyl, CH (CH 3 ) -C 2 H 5 , CH 2 -CH (CH 3 ) 2 and C (CH 3 ) 3 ;
  • - C 1 -C 6 -haloalkyl for: a C 1 -C 4 -alkyl radical as mentioned above which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example CH 2 F, CHF 2 , CF 3 , CHC1, Dichloromethyl, trichloromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2, 2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl,?
  • Ci-C ß- alkyl for: -C-C 4 alkyl as mentioned above, and 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-l-methylpropyl or l-ethyl- 2-methylpropyl, preferably methyl, eth
  • C ⁇ -C 6 -haloalkyl a C ⁇ -C 6 -alkyl radical as mentioned above which is partially or completely by, iodine of fluorine, chlorine, bromine and / or substituted, that one of said at C ⁇ -C 4 haloalkyl radicals such as as well as for 5-fluoro-1-pentyl, 5-chloro-1-pentyl, 5-bromo-1-pentyl, 5-iodo-1-pentyl, 5,5,5-trichloro-1-pentyl, undecafluoropentyl, 6- fluoro-l-hexyl, 6-chloro-l-hexyl, 6-bromo-l-hexyl, 6-iodo-l-hexyl, 6, 6, 6-trichloro-l-hexyl or dodecafluorhexyl;
  • Phenyl-C ! -C 4 -alkyl for: benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-l-yl, 2-phenylprop-l-yl, 3-phenylprop-l-yl,
  • Heterocyclyl -C ⁇ C 4 alkyl for: heterocyclylmethyl, 1-heterocyclyl-ethyl, 2-heterocyclyl-ethyl,
  • -C-C 4 alkoxy for: 0CH 3 , OC 2 H 5 , n-propoxy, OCH (CH 3 ) 2 , n-butoxy, OCH (CH 3 ) -C 2 H 5 , OCH 2 -CH (CH 3 ) 2 or OC (CH 3 ) 3 , preferably for 0CH 3 , OC 2 H 5 or OCH (CH 3 ) 2 ;
  • haloalkoxy for: a C 1 -C 4 alkoxy radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example OCH 2 F, OCHF 2 , OCF 3 , 0CH 2 C1, 0CH (C1) 2 , 0C (C1) 3 , chlorofluoroethoxy, 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-fluor
  • C ⁇ -C 4 alkylthio for: SCH 3 , SC 2 H 5 , n-propylthio, SCH (CH 3 ) 2 , n-butylthio, SCH (CH 3 ) -C 2 H 5 , SCH 2 -CH (CH 3 ) 2 or SC (CH 3 ) 3 , preferably for SCH 3 or SC 2 H 5 ;
  • C 1 -C 4 -haloalkylthio for: a C 1 -C -alkylthio radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example SCH 2 F, SCHF 2 , SCH 2 C1, SCH (C1) 2 , SC (C1) 3 , SCF 3 , chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2, 2, 2-trifluoroethylthio, 2-chloro-2-fluoroethylthio,
  • C 1 -C 4 -alkoxy-C 4 -C 4 -alkyl for: C 1 -C 4 -alkoxy - as mentioned above - substituted -CC 4 alkyl, for example for CH 2 -OCH 3 , CH 2 -OC 2 H 5 , n-propoxymethyl, CH 2 -OCH (CH 3 ) 2 , n-butoxymethyl, (l-methylpropoxy) methyl, (2-methylpropoxy) methyl, CH 2 -OC (CH 3 ) 3 , 2- (methoxy) ethyl , 2- (ethoxy) ethyl, 2- (n-propoxy) ethyl, 2- (l-methylethoxy) ethyl, 2- (n-butoxy) ethyl, 2- (l-methylpropoxy) ethyl,
  • C 1 -C 4 alkylthio -CC 4 -alkyl for: -C 4 -alkylthio - as mentioned above - substituted -CC 4 -alkyl, for example for CH 2 -SCH 3 , CH 2 -SC 2 H 5 , n-propylthiomethyl, CH 2 -SCH (CH 3 ), n-butylthiomethyl, (1-methylpropylthio) methyl,
  • (C ⁇ -C 4 alkyl) carbonyl for: C0-CH 3 , CO-C 2 H 5 , CO-CH 2 -C 2 H 5 , CO-CH (CH 3 ) 2 , n-butylcarbonyl, CO-CH ( CH 3 ) -C 2 H 5 , CO-CH 2 -CH (CH 3 ) 2 or CO-C (CH 3 ) 3 , preferably for CO-CH 3 or CO-C 2 H 5 ; (C ⁇ -C 4 haloalkyl) carbonyl for: one
  • 2,2,2-trichloroethylcarbonyl C0-C 2 Fs, 2-fluoropropylcarbonyl, 3-fluoropropylcarbonyl, 2,2-difluoropropylcarbonyl, 2,3-difluoropropylcarbonyl, 2-chloropropylcarbonyl, 3-chloropropylcarbonyl, 2,3-dichloropropylcarbonyl, 2- Bromopropylcarbonyl, 3-bromopropylcarbonyl,
  • (C ! -C 4 alkyl) carbonyloxy for: 0-CO-CH 3 , 0-CO-C 2 H 5 , 0-CO-CH 2 -C 2 H 5 , 0-CO-CH (CH 3 ) 2 , 0-CO-CH 2 -CH 2 -C 2 H 5 , 0-CO-CH (CH 3 ) -C 2 H 5 , 0-CO-CH 2 -CH (CH 3 ) 2 or 0-CO-C (CH 3 ) 3 , preferably for 0-CO-CH 3 or 0-CO-C 2 H 5 ;
  • (-C-C 4 haloalkyl) carbonyloxy for: a (-C 4 -alkyl) carbonyl radical - as mentioned above - which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example 0-CO-CH 2 F, 0-C0-CHF 2 , 0-C0-CF 3 , 0-C0-CH 2 Cl, O-CO-CH (Cl) 2 , 0-C0-C (Cl) 3 ,
  • Chlorofluoromethylcarbonyloxy dichlorofluoromethylcarbonyloxy, chlorodifluoromethylcarbonyloxy, 2-fluoroethylcarbonyloxy, 2-chloroethylcarbonyloxy, 2-bromoethylcarbonyloxy, 2-iodoethylcarbonyloxy, 2, 2-difluoroethylcarbonyloxy, 2, 2, 2-trifluorethylcarbonyloxy,
  • (-C-C 4 -alkoxy) carbonyl for: C0-0CH 3 , CO-OC 2 H 5 , n-propoxycarbonyl, CO-OCH (CH 3 ) 2 , n-butoxycarbonyl, CO-OCH (CH 3 ) - CH 5 , CO-OCH 2 -CH (CH 3 ) 2 or CO-OC (CH 3 ) 3 , preferably for CO-OCH 3 or CO-OC 2 H 5 ;
  • (C ⁇ -C 4 -alkoxy) carbonyl -CC-C alkyl for: by (-C-C 4 alkoxy) carbonyl - as mentioned above - substituted -CC-alkyl, for example for methoxycarbonylmethyl, ethoxycarbonyl-methyl, n- Propoxycarbonyl-methyl, (1-methylethoxycarbonyl) methyl1, n-butoxycarbonylmethy1, (l-methylpropoxycarbonyl) methyl, (2-methylpropoxycarbonyl) methyl1,
  • C 1 -C 4 alkylsulfinyl for: SO-CH 3 , SO-C 2 H 5 , SO-CH 2 -C 2 H 5 , SO-CH (CH 3 ) 2 , n-butylsulfinyl, SO-CH (CH 3 ) -C 2 H 5 , SO-CH 2 -CH (CH 3 ) 2 or SO-C (CH 3 ) 3 , preferably for S0-CH 3 or SO-c 2 H 5 ; -C-C-Haloalkylsulfinyl for: a -C-C 4 alkylsulfinyl radical
  • Nonafluorobutylsulfinyl preferably for SO-CF 3 , S0-CH 2 C1 or 2, 2, 2-trifluoroethylsulfinyl;
  • Nonafluorobutylsulfonyl preferably for S0 2 -CF 3 , S0 2 -CH 2 C1 or 2, 2, 2-trifluoroethylsulfonyl;
  • N, N-dipropylamino N [CH (CH 3 ) 2 ] 2 , N, N-dibutylamino,, N-di- (1-methylpropy1) amino, N, -Di- (2-meth lpropy1) amino,
  • N [C (CH 3 ) 3 ] 2 N-ethyl-N-methylamino, N-methyl-N-propylamino, N-methyl-N- (1-methylethyl) amino, N-butyl-N-methylamino,
  • Di- (-C 4 -alkyl) -aminocarbonyl for example N, N-dimethylaminocarbonyl, N, N-diethylaminocarbonyl,
  • Di- (C ⁇ -C4 alkyl) aminocarbonyl-C ⁇ -C 4 alkyl by di- (C ⁇ -C4 alkyl) aminocarbonyl monosubstituted C ⁇ -C 4 alkyl, for example, di- (C ⁇ -C 4 -alkyl) —aminocarbonylmethyl, 1- or 2-di- (-C-alkyl) —aminocarbonylethyl, 1-, 2- or 3-di- (-C-C 4 -alkyl) —aminocarbonylpropyl;
  • C 1 -C 4 -alkoxy for example di- (C 4 -alkyl) -aminocarbonylmethoxy, 1- or 2-di- (C 1 -C -alkyl) -aminocarbonylethoxy, 1-, 2- or 3-di- (C ⁇ -C alkyl) aminocarbonylpropoxy;
  • C 2 -C 6 haloalkenyl for: CC 6 alkenyl as mentioned above, which is partially or completely substituted by fluorine, chlorine and / or bromine, for example 2-chlorovinyl, 2-chloroallyl, 3-chloroallyl, 2,3- dichloroallyl,
  • C 2 -C 6 -haloalkynyl for: CC 6 -alkynyl as mentioned above, which is partially or completely substituted by fluorine, chlorine and / or bromine, for example 1, l-difluoroprop-2-in-l-yl, 1, l-difluorobut-2-in-l-yl, 4-fluorobut-2-in-l-yl, 4-chlorobut-2-in-l-yl,
  • C 3 -C 8 cycloalkyl for: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl;
  • Thiocarbonyl ring member contains e.g. for cyclobutanon-2-yl
  • C 3 -C 8 cycloalkyl -CC-C-alkyl for: cyclopropylmethyl, 1-cyclopropyl-ethyl, 2-cyclopropyl-ethyl, 1-cyclopropyl-prop-l-yl, 2-cyclopropyl-prop-l-yl, 3rd -Cyclopropyl-prop-l-yl, 1-cyclopropyl-but-l-yl, 2-cyclopropyl-but-l-yl, 3-cyclopropyl-but-l-yl, 4-cyclopropyl-but-l-yl, l -Cyclopropyl-but-2-yl, 2-cyclopropyl-but-2-yl, 3-cyclopropyl-but-2-yl, 4-cyclopropyl-but-2-yl, 1- (cyclopropylmethyl) eth-l-yl , 1- (Cyclopropylmethyl) -1- (methy1) -e
  • 3- to 7-membered heterocyclyl is understood to mean both saturated, partially or completely unsaturated and aromatic heterocycles having one, two or three heteroatoms, the heteroatoms being selected from nitrogen atoms, oxygen and sulfur atoms.
  • Saturated 3- to 7-membered heterocyclyl can also contain a carbonyl or thiocarbonyl ring member.
  • saturated heterocycles which can contain a carbonyl or thiocarbonyl ring member are:
  • unsaturated heterocycles which may contain a carbonyl or thiocarbonyl ring member are: dihydrofuran-2-yl, l, 2-oxazolin-3-yl, l, 2-oxazolin-5-yl, l, 3-oxazolin 2-yl.
  • aromatic heterocyclyl examples are 5- and
  • 6-membered aromatic, heterocyclic radicals e.g. Furyl such as 2-furyl and 3-furyl, thienyl such as 2-thienyl and 3-thienyl, pyrrolyl such as 2-pyrrolyl and 3-pyrrolyl, isoxazolyl such as 3-isoxazolyl, 4-isoxazolyl and 5-isoxazolyl, isothiazolyl such as 3-isothiazolyl, 4-isothiazolyl and 5-isothiazolyl, pyrazolyl such as 3-pyrazolyl, 4-pyrazolyl and 5-pyrazolyl, oxazolyl such as 2-0xazolyl, 4-0xazolyl and 5-0xazolyl, thiazolyl such as 2-thiazolyl, 4-thiazolyl and 5-thiazolyl, Imidazolyl such as 2-imidazolyl and 4-imidazolyl, oxadiazolyl such as l, 2,4-oxadiazol-3-y
  • fused rings are, in addition to phenyl, the aforementioned heteroaromatic groups, in particular pyridine, pyrazine, pyridazine, pyrimidine, furan, dihydrofuran, thiophene, dihydrothiophene, pyrrole, dihydropyrrole, 1,3-dioxolane, 1,3-dioxolan-2-one, isoxazole , Oxazole, oxazolinone, isothiazole, thiazole, pyrazole, pyrazoline, imidazole, imidazolinone,
  • suitable substituents on the fused ring are the meanings given below for R 15 , R 16 , R 17 and R 18 .
  • R 3 is hydrogen, chlorine or in particular fluorine
  • R 4 halogen, preferably chlorine, and cyano.
  • X, R 4 and R 5 have, independently of one another and preferably together, the following preferred meanings:
  • X is a chemical bond, methylene, ethane-1,2-diyl, ethene-1,2-diyl, which may be unsubstituted or a substituent selected from C 1 -C 4 -alkyl, especially methyl, or halogen, especially chlorine , for example 1- or 2-chloroethane-1, 2-diyl, 1- or 2-chloroethene-1, 2-diyl, 1- or 2-bromoethane-1, 2-diyl, 1- or 2-bromoethene-1, 2-diyl, 1- or 2-methylethane-1,2-diyl, 1- or 2-methylethene-1,2-diyl, especially a chemical bond, 1- or
  • variables R 7 , R 8 , R 9 , Y, Z mentioned in the definition of the variables R 5 preferably have the following meanings:
  • Y, Z independently of one another are a chemical bond or methylene
  • Ci-C ß -haloalkyl in particular hydrogen, Ci-C ß -haloalkyl, -C-C alkoxy-C -C -alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -CH (R 10 ) (R 11 ) , -C (R 10 ) (R 1: L ) -CO-OR 12 , -C (R 10 ) (R 1: 1 -) - CO-N (R 12 ) R 13 , phenyl or C 3 -C 8 Cycloalkyl, particularly preferably hydrogen,
  • R 10 , R 11 , R 12 and R 13 independently of one another preferably have the meanings given below:
  • R 10 is hydrogen or -CC 4 alkyl, especially methyl or ethyl
  • R 11 is hydrogen or -CC 4 alkyl, especially methyl or ethyl
  • R 12 , R 13 independently of one another are hydrogen, Ci-C ⁇ - alkyl, Cx-Cg-haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl,
  • C 3 -C 8 -cycloalkyl C 3 -C 8 -cycloalkyl-C 1 -C -alkyl, or -CC 4 alkoxy -CC 4 -alkyl, in particular hydrogen or -C 6 -alkyl;
  • R 9 Ci-Ce alkyl, -CC alkoxycarbonyl -CC 4 alkyl, C 2 -C 6 alkenyl, especially methyl or ethyl.
  • R 7 and R 8 independently of one another are C 3 -C 8 cycloalkyl-C 4 -C 4 -alkyl or Cx-C ⁇ - alkyl.
  • R 5 very particularly preferably represents C 3 -C 4 -alkynyloxy, C x -C 4 -alkoxy, C 3 -C 4 -alkenyloxy, OCH (R 19 ) -COOR 20 , CO-OR 21 or COO-CH (R 22 ) COOR 23 , wherein R 19 , R 22 independently of one another represent hydrogen or C ⁇ -C alkyl,
  • R 20, R 2 ⁇ , R 23 are independently C ⁇ -C alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C ⁇ -C4 haloalkyl, C ⁇ -C4-alkoxy-C ⁇ -C 4 mean alkyl;
  • R 4 and XR 5 or XR 5 and R 6 in formula I can also form a 3- or 4-membered chain which, in addition to carbon, has 1, 2 or 3, preferably 2, heteroatoms selected from nitrogen, oxygen and sulfur atoms can, which may be unsubstituted or in turn carry one, two or three substituents, and the members of which may also comprise one or two non-adjacent carbonyl, thiocarbonyl or sulfonyl groups.
  • Such connections are referred to below as connections IB and IC.
  • R 17 is hydrogen, hydroxy, C 1 -C 6 alkyl, Cx-Ce haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C -C 6 alkynyl, C 1 -C alkoxy, C 1 -C-haloalkoxy, C 3 -C 6 -alkenoxy, C 3 -C 6 -alkynyloxy, -C-C-alkylsulfonyl, -C-C-haloalkylsulfonyl, C ⁇ -C 4 -alkylcarbonyl, C ⁇ -C 4 -haloalkylcarbonyl, C ⁇ -C 4 -alkoxycarbonyl,
  • C ⁇ -C4-alkoxy-C ⁇ -C 4 alkyl C 1 -C 4 alkoxy-alkoxycarbonyl-C ⁇ -C 4 -alkyl, C 4 alkoxycarbonyl-C 1 -C 4, Mono- and di- (-C 4 -alkyl) aminocarbonyl, mono- and di- (C ⁇ -C 4 -alkyl) aminocarbonyl-C ⁇ -C -alkyl, mono- and di- (C ⁇ -C4-alkyl) aminocarbonyl- -C-C 4 -alkoxy, phenyl, phenyl-C 1 -C -alkyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkyl-C ⁇ -C 4 -alkyl, 3-, 4-, 5-, 6- or 7-membered heterocyclyl, 3-, 4-, 5-, 6- or 7-membered heterocyclyl -C-C 4 alkyl, preferably 5-
  • R 18 is hydrogen, halogen, cyano, amino, -CC 6 alkyl,
  • -C 4 -alkyl aminocarbonyl, di- (-C-C 4 -alkyl) aminocarbonyl-C ⁇ -C 4 -alkyl, di- (C ⁇ -C 4 -alkyl) aminocarbonyl-C ⁇ -C4-alkoxy, Di (C 1 -C 4 alkyl) aminocarbonyl C 1 -C 4 alkylthio, C 3 -C 8 cycloalkyl, phenyl, phenyl C 1 -C 4 alkyl, C 3 -C 8 cycloalkyl C 1 -C 4 alkyl, 3-, 4-, 5-, 6- or 7-membered, preferably 5- or 6-membered, preferably saturated heterocyclyl which has one or two, preferably a ring heteroatom, selected from oxygen, nitrogen or Sulfur.
  • R 15 to R 18 preferably have the following meanings:
  • R 15 , R 16 independently of one another are hydrogen or methyl
  • R 17 is hydrogen, hydroxy, C 1 -C 4 -alkyl, C 4 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C! -C 4 -alkoxy, -C-C 4 -haloalkoxy, C 3 -C 6 -alkenyloxy, C 3 -C 6 -alkynyloxy, -C-C -alkoxycarbonyl-C ⁇ -C 4 -alkyl, C ⁇ -C -alkoxycarbonyl- C ⁇ - C 4 -alkoxy, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkyl-C ⁇ -C 4 -alkyl or phenyl-C 1 -C-alkyl or 3-, 4-, 5- or 6-membered, preferably 5- or 6-membered, preferably saturated Heterocyclyl, which has a ring heteroatom selected from oxygen, nitrogen or
  • R 18 is hydrogen, halogen, amino, C ⁇ -C 6 -alkyl, C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl r C ⁇ -C 4 -Alkoxy, C 3 -C 6 -alkenoxy, C 3 -C 6 -alkynyloxy, -C-C 4 -alkylamino, di- (-C-C 4 -alkyl) amino, -C-C 4 -alkylthio, -C-C -alkoxycarbonyl -C-C 4 -alkyl, C 1 -C 4 -alkoxycarbonyl-C ⁇ -C 4 -alkoxy, C ⁇ -C 4 -alkoxycarbonyl-C ⁇ -C 4 -alkylthio, C 3 -C 8 cycloalkyl, phenyl, phenyl-C
  • R 4 together with XR 5 for a chain of the formula -0- [C (R 15 ) (R 16 )] n -CO-N (R 17 ) -, -S - [C (R 15 ) (R 16 )] n -C0-N (R 17 ) - with n 0 or 1.
  • R 15 and R 17 have in particular the meanings given as preferred.
  • the compounds IB are very particularly preferred in which the nitrogen atom of the chain -0-C (R 16 ) (R 15 ) -CO-N (R 17 ) - or -SC (R i6 ) (R 15 ) -C0 -N (Rl 7 ) - is bonded to the carbon atom of the phenyl ring in the formula I which bears the group XR 5 (meta position with respect to the pyridine group).
  • R 16 in these chains is preferably hydrogen.
  • R 3 preferably represents halogen and in particular fluorine, or hydrogen.
  • R 15 to R 18 have the meanings given above, in particular the meanings given as preferred.
  • the nitrogen atom of the chain is preferably bonded to the C atom of the phenyl ring in formula I which carries the group XR 5 .
  • R 3 preferably represents fluorine or hydrogen.
  • R 4 preferably represents chlorine or cyano.
  • variable XR 5 has the meanings mentioned above and in particular the meanings given in one row of Table 1 (compounds IAb.l-IAb.232 to IAq. L-IAq .232).
  • the compounds of the general formulas IAa to IAh are particularly preferred, in particular those in which X is a single bond and R 5 is -CO-OYR 7 and -OYR 7 and particularly preferably for C 3 -C 4 alkynyloxy, OCH (R 19 ) -COOR 20 , CO-OR 2! or COO-CH (R 22 ) COOR 23 , in which R 7 , R 19 to R 23 have the meanings given above.
  • the 2-aryl-5-trifluoromethylpyridines according to the invention, their N-oxides and their salts can be prepared analogously to the 2-aryl-5-trifluoromethylpyridines known from the prior art cited at the beginning.
  • a suitably substituted pyridine of the general formula II is preferably coupled
  • R a is halogen or S (0) k -phenyl, where k is 0, 1 or 2.
  • R 3 and R 4 have the meaning given above and R b stands for a substituent which is compatible with the metal atom or the semimetal and which is prepared by known processes can be converted into one of the groups XR 5 or means a group XR 5 which is compatible with the metal or the semimetal.
  • the reaction of II with III is preferably carried out in the presence of catalytically active amounts of a transition metal of the 8th subgroup of the periodic table, for example Ni or Pd, it being possible for the metal as such to be used in doped or supported form, as a complex compound or as a salt.
  • R b represents hydrogen, C 1 -C 4
  • R 'hydrogen or -CC-alkyl or two radicals R' form a chain of the formula -CH 2 -CH 2 - or -CH 2 -CH 2 -CH 2 ;
  • R 3a is hydrogen or halogen
  • R 4a halogen or C ⁇ -C 4 alkoxy
  • R 5a is hydrogen, cyano, halogen, -0-YR 7a , -O-CO-YR 7 , -SYR 7a , -CO-OYR 7 or —P0 (O-YR 7 ) 2 ; wherein R 7a represents a group -C (R 10 ) (R 1: L ) -CO-OR 12 and Y, R 7 , R 10 , R 11 and R 12 have the meanings given above;
  • R 4 stands for CN and R 5a has the following meaning:
  • R 5a cyano, halogen, -OYR 7 , -O-CO-YR 7 , -SYR 7 , -CO-OYR 7 or -PO (O-Y-R 7 ) i; wherein Y and R 7 have the meanings given above;
  • boronic acids purple are new and as important intermediates for the preparation of the 2-aryl-5-trifluoromethylpyridines of the formula I according to the invention also the subject of the present invention, in the boronic acids purple, X and Y are preferably single bonds.
  • boronic acid derivatives purple such compounds are particularly important intermediates in which R 4a is chlorine and XR 5a
  • Ni catalysts nickel (II) acetylacetonate alone or in combination with the aforementioned phosphine ligands or Ni (II) acetylacetonate with imidazolium carbene ligands, as well as complexes of nickel (II) salts with the aforementioned phosphine ligands, e.g.
  • the catalyst is usually used in a substoichiometric amount, preferably from 0.001-0.8 equivalents and particularly preferably from 0.01 to 0.5 equivalents, based on pyridine II used.
  • the molar ratio of compound II to compound III is preferably in the range from 0.95: 1 to 1: 1.5.
  • alkali metal and alkaline earth metal hydroxides alkali metal (hydrogen) carbonates and phosphates such as NaOH, NaHC0 3 , Na 2 C0 3 , KHC0 3 , K 2 C0 3 , Ba (OH) 2 , K 3 P0 4 , Alkali, alkaline earth, thallium and transition metal alcoholates such as Na ethanolate, thallium ethanolate are suitable.
  • Alkali metal fluorides such as potassium fluoride, cesium fluoride, ammonium fluoride and tetrabutylammonium fluoride are also suitable as bases. The base is usually used in an approximately stoichiometric amount or in up to 10-fold excess, based on compound II.
  • Organic solvents such as DMF, dimethyl acetamide, toluene, tetrahydrofuran (THF), dioxane and dimethoxyethane are suitable as solvents.
  • the abovementioned solvents can also be used in a mixture with water, e.g. in a ratio of approximately 5: 1 to 1: 5, preferably in a ratio of approximately 2: 1 to 1: 2 and in particular approximately 1: 1.
  • the reaction temperature is usually above the melting temperature and can be up to the boiling point of the solvent. It is preferably in the range between 50 and 150 ° C.
  • the reaction can be carried out analogously to that in JP 2000080082, WO 98 54137, WO 98 11069, WO 98/11070, and WO 98/11072 described procedures take place, so that reference is made to the disclosure of these documents at this point.
  • R 2d represents halogen, especially fluorine or chlorine.
  • Shark also means halogen, especially fluorine or chlorine.
  • R is 0-alkyl or benzyl for C ⁇ -C ⁇ .
  • R b has the meanings given above.
  • the pyridine compounds V are first prepared by reacting the dihalopyridines IV with alcohols ROH in the presence of bases or by reacting IV with the corresponding alcoholates (step i)).
  • Such implementations are known in principle and are described, for example, by Tome et al. Tetrahedron Lett. 34 (41) 1993 p. 6639, Gerster et al. J. Org. Chem. 31 1966 p. 3259 and in WO 98/11069, to which reference is hereby made.
  • the introduction of the methyl group in the 4-position of the pyridine ring in step ii) surprisingly succeeds through a two-stage reaction sequence, comprising first the metalation, in particular lithiation, of the 4-position and then the reaction of the pyridine anion thus obtained with an electrophilic methylating agent , An undesired halogen-metal exchange or the formation of undesired isomers or addition products in the 6-position is not observed.
  • this procedure opens up a route for the preparation of the compounds II and thus for the preparation of the compounds I.
  • the compounds II and the processes explained in schemes 1 and 2 are therefore also an object of the present invention.
  • the pyridine derivative V is usually set in step ii) with at least one equivalent of an organolithium compound, e.g. Methyl lithium, n-butyllithium or sec-butyllithium, or with a lithium amide such as lithium diisopropyl amide or lithium 2,2,6,6-tetramethylpiperidine (LiTMP) in an aprotic, preferably ethereal organic solvent such as tetrahydrofuran or methyl 1-tert. -butyl ether.
  • the reaction is generally carried out at temperatures below ⁇ 30 ° C., preferably in the range from ⁇ 120 ° C. to ⁇ 40 ° C. and in particular in the range from ⁇ 75 ° C.
  • methylation 1 to 20 equivalents, preferably 1 to 10 equivalents, of an electrophilic methylating agent are then generally added. In some cases it may be advantageous to add the lithiated pyridine to a solution of the electrophilic methylating agent.
  • methylating agents such as methyl halides
  • electrophilic methylating agents preferably methyl chloride, methyl bromide, methyl iodide, furthermore dimethyl sulfate, methyl tosylate and methyl triflate.
  • the pyridine compound VI is treated with a strong Lewis acid such as boron tribromide, trimethylsilyl iodide or a hydrohalic acid such as concentrated hydrobromic acid.
  • R in formula VI is benzyl
  • the ether cleavage can also be carried out by means of hydrogenolysis, e.g. by treating VI with hydrogen in the presence of a transition metal catalyst such as palladium or platinum on activated carbon or Raney nickel. The conditions for this are based on the methods known from protecting group chemistry, e.g. in Kocienski et al. "Protecting Groups", Thieme Verlag 1994.
  • step iv) which, depending on the solvent, can also be in the form of the tautomeric pyridone, is fundamentally familiar to the person skilled in the art and is usually carried out by reacting VII with a Lewis acid halogenating agent such as phosgene, thionyl chloride , Phosphorus oxychloride or phosphorus (V) chloride.
  • a Lewis acid halogenating agent such as phosgene, thionyl chloride , Phosphorus oxychloride or phosphorus (V) chloride.
  • the halogenating agent is used in equimolar amounts or in a 10-fold excess in an inert, organic solvent such as chloroform, dichloroethane, toluene or in a very large excess as a solvent.
  • the reaction temperatures are generally in the range from 20 ° C.
  • R 2d represents halogen, especially fluorine or chlorine.
  • Shark also means halogen, especially fluorine or chlorine.
  • R stands for -CC-alkyl or benzyl.
  • R b has the meanings mentioned above.
  • Sg stands for hydrogen or a protective group.
  • step i an alkoxypyridine compound V is metallized, in particular lithiated, and then reacted with CO 2 or a carbonic acid derivative to give the carboxylic acid VIII.
  • step i the same applies in step 1) to scheme ii).
  • the methods for converting carboxylic acid derivatives into A ine are known to the person skilled in the art as Hof ann, Curtius and Schmidt degradation.
  • Regarding the conditions for the Implementation is referred to, for example, Houben-Weyl Organo-Nitrogen Compounds IV, Volume E16d Part 2, pages 1160-1167, Thieme Verlag Stuttgart.
  • Steps iii), iv) and v) of Scheme 2 are carried out analogously to the steps described in Scheme 1.
  • Sg represents a protective group, i.e. is different from hydrogen
  • Sg is usually cleaved under the conditions of ether cleavage (step iii) in Schemes 1 and 2).
  • Suitable protective groups are, for example, acetyl and benzyloxycarbonyl.
  • aminopyridines II can be prepared by lithiating compound V and then reacting the lithiated pyridine with an electrophilic amination reagent such as tosyl azide, phosphoryl azide, t-butylvinylazide, hydroxylamine or 2,4-dinitrophenyl hydroxylamine ether (Scheme 2, step vi)) ,
  • electrophilic amination reagent such as tosyl azide, phosphoryl azide, t-butylvinylazide, hydroxylamine or 2,4-dinitrophenyl hydroxylamine ether
  • the phenyl-Grignard compound required for this is usually prepared starting from the corresponding phenylbromide by reaction with magnesium or a second Grignard reagent.
  • the reaction temperatures required for this only open access to those Grigard compounds in which the group R 4 or R b in formula III represents a radical which does not react with a Grignard compound.
  • the corresponding phenyl iodides are first converted into Grignard compounds.
  • the conversion of functionalized aromatic iodides to Grignard reagents is basically known from the literature (see, for example, Knöchel et al, Angew. Che. 1998, 110, p. 1801 and DE-A 19836408) and is usually carried out by reacting the phenyl iodides with others Grignard.
  • the conversion of the phenylgrignard compounds III obtained in this way into the boronic acids purple then takes place at low temperatures, ie below 0 ° C., in particular at ⁇ 10 ° C. and below, that is to say at temperatures at which a number of groups which are reactive toward Grignard compounds, such as carboxylic acid ester groups, , Amide and nitrile groups, are not yet attacked.
  • the present invention also relates to the phenylboronic acid compounds of the general formula purple defined above. Depending on the processing and storage, these compounds can either be present only as monomers boronic acid or as their trimers boroxins or also as mixtures and can be used in the reactions described at the outset.
  • the corresponding iodides are first converted into the corresponding phenylgrignard compound using another Grignard compound.
  • alkyl grignard compounds for example C 1 -C 4 -alkyl magnesium halides, in particular the bromides such as methyl magnesium bromide or isopropyl magnesium bromide.
  • the iodide is used at temperatures between -78 ° C and 0 ° C, preferably at -60 ° C to 0 ° C and very particularly preferably at -50 ° C to -10 ° C with an approximately equivalent amount, for example 1 to 1.05 equivalent of a Grignard compound, preferably isopropyl magnesium bromide or chloride in an inert organic solvent, preferably an ether such as diethyl ether, tetrahydrofuran, dioxane , Dimethoxyethane, methyl tert-butyl ether or mixtures thereof.
  • the Grignard compound is then trapped at these temperatures with boric acid esters, preferably lower alkyl esters, very preferably trimethyl borate. Acidic, aqueous workup then provides the boronic acid or its trimers or, in the case of neutral workup, the esters of boronic acid (R 'H).
  • boronic acids III The iodides required for the preparation of boronic acids III are partly. known in the literature (e.g. 2-fluoro-4-chloro-5-carboisopropoxy-1-iodobenzene, CAS no .: 264927-52-8), 2-fluoro-4-chloro-5-methoxy-1-iodobenzene (CAS no .: 174913-22-5), 2-fluoro-4-chloro-l-iodobenzene (CAS no .: 6797-79-1) or can be prepared in analogy to these (see also Houben -Weyl Vol 5/4, S 639 ff).
  • Table 5 gives an example of some boronic acids according to the invention that can be produced in this way:
  • the compounds of formula I according to the invention can be prepared by derivatizing other 2-aryl-5-trifluoromethylpyridines.
  • L is a is a nucleophilically displaceable leaving group, for example a halogen atom, an arylsulfonate group, a sulfate group or comparable, preferably alkylated in the presence of a base.
  • Strong Lewis acids such as boron tribromide and hydrogen halide acids such as HBr or HI are suitable for cleaving the methyl ethers.
  • the methoxy compound is preferably reacted with 1 to 5 equivalents of the Lewis acid in an aprotic organic solvent, preferably a chlorinated hydrocarbon such as dichloromethane, chloroform or 1,2-dichloroethane.
  • the reaction temperature is usually above the melting temperature and can be up to the boiling point of the solvent. It is preferably in the range from 0 ° C to 50 ° C. Further methods and conditions for ether cleavage are described in Kocienski, "Protecting Groups", Thieme Verlag Stuttgart 1994.
  • nitration reagents come, for example, nitric acid in different concentrations, also concentrated and fuming nitric acid, mixtures of sulfuric acid and nitric acid, and salts of nitric acid such as.
  • the reaction can be carried out either in a solvent-free manner in an excess of the nitrating reagent or in an inert solvent or diluent, water, mineral acids, organic acids, halogenated hydrocarbons such as methylene chloride, anhydrides such as acetic anhydride and mixtures of these solvents being suitable, for example.
  • the reaction temperature is normally from -100 ° C to 200 ° C, preferably from -30 ° C to 50 ° C.
  • the reduction is generally carried out by reacting the nitro compound with a metal such as iron, zinc or tin under acidic reaction conditions or with a complex hydride such as lithium aluminum hydride and sodium borohydride, the reduction in bulk or in a solvent or diluent is carried out.
  • a metal such as iron, zinc or tin under acidic reaction conditions or with a complex hydride such as lithium aluminum hydride and sodium borohydride
  • a complex hydride such as lithium aluminum hydride and sodium borohydride
  • the reduction in bulk or in a solvent or diluent is carried out.
  • the following solvents e.g. Water, alcohols, such as methanol, ethanol and isopropanol, or ethers, such as diethyl ether, methyl tert-butyl ether, dioxane, tetrahydrofuran and ethylene glycol dimethyl ether, are suitable.
  • the procedure is preferably solvent-free in an inorganic acid, especially in concentrated or dilute hydrochloric acid, or in a liquid organic acid such as acetic acid or propionic acid.
  • the acid can also be diluted with an inert solvent, for example one of the abovementioned.
  • the reduction with complex hydrides is preferably carried out in a solvent, for example an ether or an alcohol.
  • the amount of acid is not critical. In order to reduce the starting compound as completely as possible, it is expedient to use at least an equivalent amount of acid.
  • the reaction temperature is generally in the range from -30 ° C. to 200 ° C., preferably in the range from 0 ° C. to 80 ° C.
  • the reaction mixture is usually diluted with water and the product by filtration, crystallization or extraction with a solvent which is largely immiscible with water, e.g. isolated with ethyl acetate, diethyl ether or methylene chloride. If desired, the product can then be cleaned as usual.
  • Suitable catalysts for this are, for example, Raney nickel,
  • the reaction solution can be worked up to the product in the customary manner.
  • the hydrogenation can be carried out under normal hydrogen pressure or under elevated hydrogen pressure.
  • amino compounds thus obtained can in turn be used with known electrophiles, e.g. with alkylsulfonic acid halides or with the corresponding anhydrides to give the sulfonamides, with alkyl halides to give the secondary and tertiary anilines.
  • a nitrous acid ester such as tert.
  • butyl nitrite and isopentyl nitrite under anhydrous reaction conditions for example in glacial acetic acid containing hydrogen chloride, in absolute alcohol, in dioxane or tetrahydrofuran, in acetonitrile or in acetone.
  • a copper (I) salt such as copper (I) cyanide, chloride, -bromide and -iodide, or with an alkali metal salt solution.
  • a copper (II) salt such as copper (II) sulfate can have an advantageous effect on the course of the reaction. In general, this reaction is carried out at 0 ° C to 100 ° C, preferably at the boiling point of the reaction mixture.
  • Meerwein arylation is usually the reaction of the diazonium salts with alkenes or alkynes.
  • the alkene or alkyne is preferably used in excess, up to about 3000 mol%, based on the amount of the diazonium salt.
  • reaction temperatures are normally from -30 ° C. to 50 ° C.
  • All reactants are preferably used in approximately stoichiometric amounts, but an excess of one or the other component, up to approximately 3000 mol%, can also be advantageous.
  • Useful reducing agents are, for example, transition metals such as iron, zinc and tin (cf., for example, "The Chemistry of the Thiol Group", John Wiley, 1974, p. 216).
  • Halosulfonation can be carried out without solvent in excess sulfonating reagent or in an inert solvent / diluent, e.g. in a halogenated hydrocarbon, an ether, an alkyl nitrile or a mineral acid.
  • Chlorosulfonic acid is both the preferred reagent and a suitable solvent.
  • the reaction temperature is usually between 0 ° C and the boiling point of the reaction mixture.
  • the reaction mixture is mixed with water, for example, after which the product can be isolated as usual.
  • the latter can be obtained particularly effectively by the above-described couplings of pyridines II with purple boronic acids.
  • C ⁇ _ 4 -Alkyl ⁇ produce.
  • the phosphonium salts, phosphonates or phosphorylides required as reactants are known or can be prepared in a manner known per se ⁇ cf. see, for example, Houben-Weyl, Methods of Organic Chemistry, Vol. El, pp. 636ff. and Vol. E2, pp. 345ff., Georg Thieme Verlag Stuttgart 1982; Chem. Ber. 95, 1962, 3993 ⁇ .
  • the required amino (thio) phenols IA can be prepared using the methods described under II.
  • Table 6 shows examples of preferred aminophenols of the general formula IAr, in which R 1 , R 2 and R 3 have the abovementioned and in particular the meanings given in Table 6: Table 6:
  • the compounds IB obtainable in this way, in which R i7 is hydrogen, can be prepared by known processes, as described, for example, in WO 95/02590, WO 98/07700 and the prior art cited therein in Sicker et al. Tetrahedron 52, 1996, 10389 or in DE-A 19508590 are described, with an alkylating agent R 27 '-! implement.
  • L stands for a nucleophilically displaceable leaving group such as halogen, aryl sulfonate, triflate or sulfate or for an isocyanate group.
  • L7 R ' represents, for example C ⁇ -C 6 -alkyl, C 6 haloalkyl, C 2 -C 6 alkenyl, C -C 6 haloalkenyl, C 2 -C 6 alkynyl, C ⁇ -C 4 alkylsulfonyl, C ⁇ -C 4 -haloalkylsulfonyl, C ⁇ -C 4 -alkylcarbonyl, C ⁇ -C 4 -haloalkylcarbonyl, C ⁇ -C 4 -alkoxycarbonyl, C ⁇ -C -alkoxy-C ⁇ -C -alkyl, C ⁇ -C 4 -alkoxycarbonyl-C ⁇ -C 4- alkyl, mono- and
  • the compounds I in which the radicals XR 5 and R 4 are a chain of the formula -0-C (R 15 , R i6 ) -CO-NR i7 - or -SC (R i5 , R i6 ) -CO-NRi 7 - Form, can also be obtained by reductive cyclization of nitrophenoxycarboxylic acid derivatives of the general formula IAs or corresponding nitrothiophenoxycarboxylic acid derivatives.
  • R 1 , R 2 , R 3 , R i5 , R i6 and R 17 ' have the abovementioned meanings.
  • R X9 stands for alkyl with preferably 1 to 4 carbon atoms, in particular methyl or ethyl.
  • the variable 1 stands for 0 or 1.
  • step i) stands for the reductive cyclization and step ii) for the above-described reaction with the electrophile L-RI 7 '.
  • Table 7 shows, by way of example, preferred nitrophenoxyalkane carboxylic acid derivatives of the general formula IAs, in which R X5 and R 16 are hydrogen and R 1 , R 2 , R 3 and R 19 have the meanings indicated above and in particular those mentioned in Table 7, and Of particular importance as intermediates for the preparation of compound B are: Table 7;
  • Preferred halogen is chlorine or bromine; sodium thiocyanate is preferred among the alkali / alkaline earth metal thiocyanates.
  • an inert solvent / diluent e.g. in a hydrocarbon such as toluene and hexane, in a halogenated hydrocarbon such as dichloromethane, in an ether such as tetrahydrofuran, in an alcohol such as ethanol, in a carboxylic acid such as acetic acid, or in an aprotic solvent such as dimethylformamide, acetonitrile and dimethyl sulfoxide.
  • the reaction temperature is usually above that
  • Melting temperature and can be up to the boiling point of the solvent. It is preferably in the range from 0 to 150 ° C.
  • Chain -SC (R 8 ) N- with nitrogen bound via the ⁇ -C atom.
  • M ® stands for an alkali metal ion or 1/2 alkaline earth metal ion.
  • the information given above applies to carrying out the diazotization.
  • an inert solvent for example an ether such as tetrahydrofuran and dioxane, an aprotic solvent such as dimethylformamide and acetonitrile, a coal Hydrogen such as toluene and hexane, a halogenated hydrocarbon such as dichloromethane, or solvent-free
  • the reaction is preferably carried out at elevated temperature, for example at the boiling point of the reaction mixture.
  • Oxidizing agents customary for converting the pyridines I into their N-oxides are e.g. Peracetic acid, trifluoroperacetic acid, perbenzoic acid, meta-chloroperbenzoic acid, magnesium monoperphthalate, 1,2-dicarboxylic acid derivatives in general, sodium perborate, oxones (contains peroxodisulfate), per tungstic acid, hydrogen peroxide, methyltrioxorhenium. These reagents can be used alone or in a mixture.
  • the oxidation is preferably carried out in a solvent or diluent.
  • Suitable solvents are water, sulfuric acid, carboxylic acids such as e.g. Acetic acid, and halogenated solvents such as e.g. Dichloromethane and chloroform or mixtures of the above Solvent.
  • the reaction is normally carried out in the temperature range from 0 ° C. to the boiling point of the solvent, preferably up to 150 ° C.
  • the oxidizing agents are normally used in at least an equimolar amount, often in large excess, for example up to 5 equivalents, based on the pyridine I to be oxidized.
  • Protective groups suitable for this purpose and the conditions suitable for introduction and cleavage can be found in Cocienski, "Protecting Groups", Thieme Verlag Stuttgart 1994. Examples of suitable protective groups include benzyloxycarbonyl and fluorenylmethoxycarbonyl.
  • 2-fluoro-4-chloro-5-methoxy-phenylboronic acid 1.1 g (0.001 mol) tetrakistriphenylphosphine palladium and 12.0 g sodium hydrogen carbonate in 150 mL THF and 150 mL water for 20 hours under reflux. After cooling, the phases were separated, the aqueous phase was extracted twice with 100 ml each of methyl tert-butyl ether, the combined organic phases were dried over sodium sulfate and concentrated in vacuo.
  • reaction mixture was then added dropwise to a solution of 17.2 g (0.1 mol) of potassium iodide in 30 ml of water.
  • the mixture was first allowed to warm to room temperature and then heated to 60 to 70 ° C. for 30 minutes. After cooling, the mixture was extracted three times with 200 mL methylene chloride, 45 the combined organic phases were dried over sodium sulfate. fat and constricted.
  • 27.6 g of 2-chloro-4-fluoro-5-iodobenzoic acid isopropyl ester with a melting point of 38 to 43 ° C. were obtained.
  • Example 7 2- (2-fluoro-4-chloro-5- (2-chloro-2-carbomethoxyethyl) phenyl) -3-chloro-4-methyl-5-trifluoromethylpyridine (IAa .199)
  • Example 8 2- (2-fluoro-4-chloro-5-hydroxycarbonyl-phenyl-1-yl) -3-chloro-4-methyl-5-trifluoromethylpyridine (IAa.124)
  • Example 9 2- [2-fluoro-4-chloro-5- (2-methoxycarbonylpropionyl) carbonyl-phenyl-1-yl] -3-chloro-4-methyl-5-trifluoromethyl-pyridine (compound IAa.143 as R enantiomer and as S enantiomer)
  • Example 1.5 The title compound was prepared analogously to the procedure described in Example 1.5. Starting from 1.8 g (7.7 mol) of pyridine from Example 1.4 and 1.5 g (7.7 mmol) of cyanoboronic acid from Example 11.1, 1.0 g of the title compound with mp. 108 to 109 ° C. was obtained.
  • Example 12 2- [2-fluoro-4- (methoxycarbonyl) methoxy-5-nitrophenyl] -3-chloro-4-methyl-5-trifluoromethylpyridine (comp. Las.5)
  • Example 13 7- (3-chloro-4-methyl-5-trifluoromethyl-pyridine-2-yl) -6-fluoro-2H-l, 4-benzoxazin-3-one (IBa. 1)
  • Example 14 7- (3-chloro-4-methyl-5-trifluoromethylpyridin-2-yl) -6-fluoro-4-propargyl-2H-l, 4-benzoxazin-3-one (IBa .24)
  • Example 16 4-Chloro-7- [3-chloro-4-methyl-5- (trifluoromethyl) -2-pyridinyl] -2-ethyl-6-fluoro-1,3-benzoxazole (ICe.3)
  • Example 17 2- (2-fluoro-4-chloro-5-methoxy-phenyl-l-yl) -3-chloro-4-amino-5-trifluormethylpyridine (IAi .3)
  • the compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides.
  • the herbicidal compositions containing I control vegetation very well on non-cultivated areas, particularly when high amounts are applied. In crops such as wheat, rice, corn, soybeans and cotton, they act against weeds and grass weeds without significantly damaging the crop plants. This effect occurs especially at low application rates.
  • the compounds I or compositions containing them can also be used in a further number of crop plants for eliminating undesired plants.
  • the following crops are considered, for example:
  • the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
  • 3-halo-2-phenylpyridines and their agriculturally useful salts are also suitable for the desiccation and / or defoliation of plants.
  • desiccants they are particularly suitable for drying out the aerial parts of crops such as potatoes, rapeseed, sunflower and soybeans. This enables a fully mechanical harvesting of these important crops.
  • the waste promoted by the use of compounds of the formula I according to the invention and their agriculturally useful salts is based on the formation of separating tissue between the fruit or leaf and shoot part of the plants.
  • Cotton demonstration is of particular economic interest because it makes harvesting easier.
  • the shortening of the time interval in which the individual plants mature leads to an increased quality of the harvested fiber material.
  • the compounds I or the compositions comprising them can be sprayed, for example in the form of directly sprayable aqueous solutions, powders, suspensions, including high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprays or granules. Misting, dusting, scattering, watering or treating the seed or mixing with the seed can be used.
  • the application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • the herbicidal compositions comprise a herbicidally effective amount of at least one compound of the formula I or an agriculturally useful salt of I and auxiliaries customary for the formulation of crop protection agents.
  • Mineral oil fractions from medium to high boiling point such as kerosene or diesel oil, also coal tar oils and oils from vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alky- gelled benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, e.g. B. amines such as N-methylpyrrolidone or water.
  • aliphatic, cyclic and aromatic hydrocarbons e.g. paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alky- gelled benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • the 3-halogeno-2-phenylipyridines 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 agent, adhesive, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
  • alkali, alkaline earth, ammonium salts of aromatic sulfonic acids e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols as well as of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its Derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tributyl
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • Granules for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers.
  • Solid carriers are mineral soils such as silica, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, Ammonium nitrate, ureas and vegetable products such as flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • the concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range.
  • the formulations generally contain 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • the compounds I according to the invention can be formulated, for example, as follows:
  • I 20 parts by weight of compound no. IAa.3 are dissolved in a mixture consisting of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil.
  • aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.
  • V 3 parts by weight of active ingredient no. IAi.10 are mixed with 97 parts by weight of finely divided kaolin. In this way, a dust is obtained which contains 3% by weight of the active ingredient.
  • VI 20 parts by weight of active ingredient No. IBa.24 are intimately mixed with 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.
  • the herbicidal compositions or the active compounds can be applied pre-emergence, post-emergence or together with the seeds of a crop. It is also possible to apply the herbicidal compositions or active ingredients by spreading seeds of a crop plant which have been pretreated with the herbicidal compositions or active ingredients. If the active ingredients are less compatible with certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not struck wherever possible, while the active ingredients are applied to the leaves of undesirable plants growing below them or the uncovered floor area (post-directed, lay-by).
  • the application rates of active ingredient are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (a.s.), depending on the control target, the season, the target plants and the growth stage.
  • the 3-halo-2-phenylipyridines can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together.
  • Plastic pots with loamy sand with about 3.0% humus as substrate served as culture vessels.
  • the seeds of the test plants were sown separately according to species.
  • the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles.
  • the tubes were lightly sprinkled to promote germination and growth, and then covered with clear plastic hoods until the plants had grown. This cover causes the test plant, unless this was affected by the active ingredients.
  • test plants were first grown to a height of 3 to 15 cm, depending on the growth habit, and then treated with the active ingredients suspended or emulsified in water.
  • the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days before the treatment.
  • the application rate for post-emergence treatment was 31.3, 15.6, 7.8 and / or 3.9 g a. S./ha.
  • the plants were kept at temperatures of 10 - 25 ° C or 20 - 35 ° C depending on the species.
  • the trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to each treatment was evaluated.
  • Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.
  • the plants used in the greenhouse experiments are composed of the following types:
  • Table 8 The herbicidal activity found in the post-emergence process is summarized in Tables 8 and 9. Table 8:
  • Compound No. IAa.10 showed application rates of 7.8 and 3 ⁇ 3.9 g a. S./ha in the post-emergence process a significantly better effect against the harmful plants ECHCG, SETFA and BIDPI than comparative example VB.
  • Compound no. ICe.3 showed a significantly better activity against the harmful plants BRAPL, SETFA and BIDPI than comparative example VC at application rates of 7.8 and 3.9 35 g aS / ha in the post-emergence process.
  • the young cotton plants were treated to runoff with aqueous preparations of the active ingredients (with the addition of 0.15% by weight of the fatty alcohol alkoxylate Plurafac® LF 700, based on the spray mixture).
  • the amount of water applied was the equivalent of 1000 L / ha. After 13 days, the number of leaves dropped and the degree of defoliation in% were determined.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pyridine Compounds (AREA)

Abstract

L'invention concerne la 2-aryl-5-trifluorométhylpyridine de formule générale (I) dans laquelle les variables R<1>, R<2> ont les significations suivantes : R<1> NH2 ou CH3; R<2> halogène; et dans laquelle les variables R<1>, R<2>, R<3>, R<4>, R<5>, R<6> et X ont les significations spécifiées dans la revendication 1, ainsi que leurs sels compatibles avec l'emploi en agriculture. L'invention concerne en outre l'utilisation des composés (I) et de leurs sels comme herbicides et/ou pour la dessiccation et/ou la défoliation des plantes, ainsi que les agents herbicides et les produits pour la dessiccation et/ou la défoliation des plantes, renfermant, comme substances actives, les composés (I) et/ou leurs sels.
EP01995651A 2000-11-22 2001-11-21 2-aryl-5-trifluoromethylpyridine Withdrawn EP1335903A1 (fr)

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CL2008000985A1 (es) 2007-04-06 2008-10-10 Neurocrine Biosciences Inc Compuesto derivado de heterociclos de nitrogeno, agonistas del receptor gnrh; composicion farmaceutica que comprende a dicho compuesto; y uso para tratar una afeccion relacionada con las hormonas sexuales, endometriosis, dismenorrea, enfermedad de ov
AU2009259330A1 (en) 2008-06-18 2009-12-23 Basf Se 1,2-benzisothiazole compounds useful for combating animal pests
CN103221409B (zh) 2010-10-01 2016-03-09 巴斯夫欧洲公司 除草的苯并*嗪酮类
US20140187777A1 (en) * 2012-03-26 2014-07-03 Dow Agrosciences Llc Materials and methods for the base-assisted synthesis of substituted heteroaromatic compounds
US10668270B2 (en) 2013-05-06 2020-06-02 Medtronic, Inc. Substernal leadless electrical stimulation system
CN111356693A (zh) 2017-11-23 2020-06-30 巴斯夫欧洲公司 除草的苯基醚类
AU2018373436C1 (en) 2017-11-23 2023-10-19 Basf Se Herbicidal pyridylethers
WO2023044364A1 (fr) 2021-09-15 2023-03-23 Enko Chem, Inc. Inhibiteurs de protoporphyrinogène oxydase
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DE4323916A1 (de) * 1993-07-16 1995-01-19 Basf Ag Substituierte 2-Phenylpyridine
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DE19605766A1 (de) * 1996-02-16 1997-08-21 Basf Ag Substituierte 2-Phenylpyridine
DE19633746A1 (de) * 1996-08-22 1998-02-26 Basf Ag Substituierte 2-Phenylpyridine
EP0984933A1 (fr) * 1997-05-30 2000-03-15 Basf Aktiengesellschaft 2-phenylpyridines substituees, leur fabrication et leur utilisation comme herbicides
EP0998472A1 (fr) * 1997-07-14 2000-05-10 Basf Aktiengesellschaft 2-(benzaryl)pyridines substituees

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