WO2011058036A1 - Composés tricycliques ayant un effet herbicide - Google Patents

Composés tricycliques ayant un effet herbicide Download PDF

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WO2011058036A1
WO2011058036A1 PCT/EP2010/067176 EP2010067176W WO2011058036A1 WO 2011058036 A1 WO2011058036 A1 WO 2011058036A1 EP 2010067176 W EP2010067176 W EP 2010067176W WO 2011058036 A1 WO2011058036 A1 WO 2011058036A1
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formula
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Dschun Song
Julia Major
Johannes Hutzler
Trevor William Newton
Thomas Ehrhardt
Klaus Kreuz
Klaus Grossmann
Anna Aleksandra Michrowska-Pianowska
Anja Simon
Richard Roger Evans
Matthias Witschel
William Karl Moberg
Liliana Parra Rapado
Tao QU
Frank Stelzer
Andree Van Der Kloet
Thomas Seitz
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
    • C07D471/14—Ortho-condensed systems

Definitions

  • Tricyclic compounds having herbicidal action Description
  • the present invention relates to tricyclic compounds of the formula I
  • R 1 is 0-R A , S(0) n -R A or 0-S(0) n -R A ;
  • R A is hydrogen, Ci-C4-alkyl, Z-C3-C6-cycloalkyl, Ci-C4-haloalkyl,
  • R a is hydrogen, OH, d-Cs-alkyl, Ci-C 4 -haloalkyl, Z-C 3 -C 6 -cycloalkyl, C2-Cs-alkenyl, Z-Cs-Ce-cycloalkenyl, C2-Cs-alkynyl, Z-Ci-C6-alkoxy, Z-Ci-C 4 -haloalkoxy, Z-Cs-Cs-alkenyloxy, Z-Cs-Cs-alkynyloxy,
  • NR'R d-Ce-alkylsulfonyl, Z-(tri-Ci-C 4 -alkyl)silyl, Z-phenyl, Z-phenoxy, Z-phenylamino or a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic heterocycle which contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S, where the cyclic groups are unsubstituted or substituted by 1 , 2, 3,
  • R', R" independently of one another are hydrogen, Ci-Cs-alkyl, Ci-C 4 -haloalkyl, Cs-Cs-alkenyl, Cs-Cs-alkynyl,
  • R' and R" together with the nitrogen atom to which they are attached may also form a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic heterocycle which contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S;
  • Z is a covalent bond or Ci-C4-alkylene;
  • n 0, 1 or 2;
  • R 2 is phenyl, naphthyl or a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic aromatic heterocycle which contains 1 , 2, 3, 4 or 5 heteroatoms selected from the group consisting of O, N and S, where the cyclic groups are
  • R b independently of one another are Z-CN, Z-OH, Z-NO2, Z-halogen,
  • d-Cs-alkyl Ci-C 4 -haloalkyl, C 2 -C 8 -alkenyl, C 2 -C 8 -alkynyl,
  • R bb is Ci-Cs-alkyl or Ci-C 6 -haloalkyl and n is 0, 1 or 2;
  • R b together with the group R b attached to the adjacent carbon atom may also form a five- or six-membered saturated or partially or fully unsaturated ring which, in addition to carbon atoms, may contain 1 , 2 or 3 heteroatoms selected from the group consisting of O, N and S;
  • A, E, G, M are N or C-R c , one or two of these groups being N;
  • R c is hydrogen or one of the groups mentioned for R b ;
  • R 3 , R 4 independently of one another are a group R c or the two groups together are a double bond;
  • W, U independently of one another are N and C-R c ;
  • the invention relates to processes and intermediates for preparing the compounds of the formula I and the N-oxides thereof, the agriculturally usable salts thereof, and also to active compound combinations comprising them, to compositions comprising them and to their use as herbicides, i.e. for controlling harmful plants, and also to a method for controlling unwanted vegetation which comprises allowing a herbicidally effective amount of at least one compound of the formula I or of an agriculturally suitable salt of I to act on plants, their seed and/or their habitat.
  • WO 2008/009908 and WO 2008/071918 describe herbicidal pyridopyrazines; however, their herbicidal action at low application rates and/or their compatibility with crop plants leave scope for improvement.
  • active compounds having strong herbicidal action in particular even at low application rates, whose compatibility with crop plants is sufficient for commercial application.
  • the compounds according to the invention can be prepared from the compounds of the formula II described in WO 2009/090401 and WO 2009/090402 using standard methods of organic chemistry, for example by the synthesis route described below.
  • the compounds of the formula I in which W and U are C-R c can be obtained, for example, as follows. Pyridones of the formula II can be reacted with amines of the formula III to give compounds of the formula IV.
  • the variables have the meaning given for formula I.
  • the group R is C1-C6 alkyl, such as, preferably, methyl or ethyl.
  • This reaction is usually carried out at temperatures of from -78°C to 180°C, preferably from 20°C to 150°C, in an inert organic solvent in the presence of a base such as, for example, hexamethyldisilazane (cf. Org. Process Res. Dev. 2008, 12, 1261 -1264; WO 99/40090).
  • a base such as, for example, hexamethyldisilazane (cf. Org. Process Res. Dev. 2008, 12, 1261 -1264; WO 99/40090).
  • Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and
  • chlorobenzene ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran (THF), nitriles, such as acetonitrile and propionitrile, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and also dimethyl sulfoxide (DMSO), dimethylformamide (DMF) and dimethylacetamide (DMA). It is also possible to use mixtures of the solvents mentioned.
  • ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran (THF)
  • nitriles such as acetonitrile and propionitrile
  • alcohols such as methanol
  • Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides, such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls, such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides, such as methylmagnesium chloride, and also alkali metal and alkaline earth metal alkoxides
  • the starting materials are generally reacted with one another in equimolar amounts.
  • the compounds of the formula IV can be cyclized directly to the unsaturated compounds of the formula ⁇ in which W and U are C-R c and R 3 and R 4 together are a double bond
  • This reaction is usually carried out at temperatures of from -78°C to 100°C, preferably from 10°C to 50°C, in an inert organic solvent in the presence of an acid or a Lewis acid or a catalyst, such as, for example, 0.5 N HCI in water/THF [cf.: Helv. Chim. Acta 1986, 69(8), 1887-97].
  • an acid or a Lewis acid or a catalyst such as, for example, 0.5 N HCI in water/THF [cf.: Helv. Chim. Acta 1986, 69(8), 1887-97].
  • Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and
  • chlorobenzene ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and THF, nitriles, such as acetonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, water, and also DMSO, DMF and DMA. It is also possible to use mixtures of the solvents mentioned.
  • ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and THF
  • nitriles such as acetonitrile and propionitrile
  • ketones
  • Suitable for use as acids and acidic catalysts are inorganic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid,
  • Lewis acids such as boron trifluoride, aluminum trichloride, iron(lll) chloride, tin(IV) chloride, titanium(IV) chloride and zinc(ll) chloride, Lewis-acidic solids, such as zeolites, silicates, and also organic acids, such as formic acid, acetic acid, propionic acid, oxalic acid, toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid and trifluoroacetic acid.
  • Lewis acids such as boron trifluoride, aluminum trichloride, iron(lll) chloride, tin(IV) chloride, titanium(IV) chloride and zinc(ll) chloride, Lewis-acidic solids, such as zeolites, silicates, and also organic acids, such as formic acid, acetic acid, propionic acid, oxalic acid, toluenesulfonic acid, benzenesulfonic
  • the compounds of the formula Ila can be converted by reaction with amines of the formula III initially into the acetals of the formula IVa.
  • This reaction is usually carried out at temperatures of from -78°C to 180°C, preferably from 20°C to 120°C, in an inert organic solvent [cf.: J. Het. Chem. 2008, 45(6), 1665-1672].
  • Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and
  • chlorobenzene ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and THF, nitriles, such as acetonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butylmethyl ketone, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, water, and also DMSO, DMF and DMA. It is also possible to use mixtures of the solvents mentioned.
  • ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and THF
  • nitriles such as acetonitrile and propionitrile
  • ketones such
  • X 1 is a nucleophilic leaving group, such as, for example, halogen, alkyl sulfate or alkylsulfonate.
  • keto compounds of the formula IVb can be released from the acetals of the formula IVa.
  • This reaction is usually carried out at temperatures of from -78°C to 100°C, preferably from 10°C to 50°C, in an inert organic solvent in the presence of an acid or a Lewis acid or a catalyst, such as, for example, 0.5 N HCI in water/THF [cf.: Helv. Chim. Acta 1986, 69(8), 1887-97].
  • an acid or a Lewis acid or a catalyst such as, for example, 0.5 N HCI in water/THF [cf.: Helv. Chim. Acta 1986, 69(8), 1887-97].
  • Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and
  • chlorobenzene ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and THF, nitriles, such as acetonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, water, and also DMSO, DMF and DMA. It is also possible to use mixtures of the solvents mentioned.
  • ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and THF
  • nitriles such as acetonitrile and propionitrile
  • ketones
  • Suitable for use as acids and acidic catalysts are inorganic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid,
  • Lewis acids such as boron trifluoride, aluminum trichloride, iron(lll) chloride, tin(IV) chloride, titanium(IV) chloride and zinc(ll) chloride, Lewis-acidic solids, such as zeolites, silicates, and also organic acids, such as formic acid, acetic acid, propionic acid, oxalic acid, toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid and trifluoroacetic acid.
  • Lewis acids such as boron trifluoride, aluminum trichloride, iron(lll) chloride, tin(IV) chloride, titanium(IV) chloride and zinc(ll) chloride, Lewis-acidic solids, such as zeolites, silicates, and also organic acids, such as formic acid, acetic acid, propionic acid, oxalic acid, toluenesulfonic acid, benzenesulfonic
  • the cyclization of IVb to compounds of the formula ⁇ . ⁇ can be carried out using, for example, ammonia.
  • This reaction is usually carried out at temperatures of from -120°C to 0°C, preferably from -78°C to -33°C, in an inert organic solvent in the presence of ammonia [cf.:
  • Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and
  • chlorobenzene ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and THF, nitriles, such as acetonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and also DMSO, DMF and DMA. It is also possible to use mixtures of the solvents mentioned.
  • ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and THF
  • nitriles such as acetonitrile and propionitrile
  • ketones such as
  • a further preparation method for compounds of the formula I proceeds via a 2-halo- pyridine intermediate of the formula IVc.
  • X is halogen, preferably chlorine or bromine, in particular chlorine.
  • This reaction is carried out in the presence of a halogenating agent, usually at temperatures of from -78°C to 150°C, preferably from 0°C to 100°C, in an inert organic solvent and in the presence of a base [cf.: Eur. J. Med. Chem. 2009, 44, 954-958].
  • Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and
  • chlorobenzene ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and THF, nitriles, such as acetonitrile and propionitrile, and also DMSO, DMF and DMA. It is also possible to use mixtures of the solvents mentioned.
  • Suitable halogenating agents are, in particular, phosphorus halides, phosphorus oxychlorides, such as PCI 3 , PCI 5 , POCI 3 , PBr 3 , PBr 5 .
  • Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides, such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate, calcium carbonate, cesium carbonate and rubidium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls, such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides, such as methylmagnesium chloride, and also alkali metal
  • amines such as triethylamine, diisopropylethylamine.
  • bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.
  • the starting materials are generally reacted with one another in equimolar amounts.
  • the compounds of the formula IV can also be prepared by reacting co
  • This reaction is usually carried out at temperatures of from -78°C to 180°C, preferably from 20°C to 130°C, in an inert organic solvent and in the presence of a base [cf.: J. Het. Chem. 1991 , 28(4), 971 -6].
  • Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, nitriles, and also DMSO, DMF and DMA, particularly preferably DMSO. It is also possible to use mixtures of the solvents mentioned.
  • Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal oxides, alkali metal and alkaline earth metal hydrides, alkali metal amides, alkali metal and alkaline earth metal carbonates, and also alkali metal bicarbonates, organometallic compounds, in particular alkali metal alkyls, alkylmagnesium halides, and also alkali metal and alkaline earth metal alkoxides and dimethoxymagnesium, moreover organic bases, for example tertiary amines, pyridine, substituted pyridines, and also bicyclic amines.
  • inorganic compounds such as alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal oxides, alkali metal and alkaline earth metal hydrides, alkali metal amides, alkali metal and alkaline earth metal carbonates, and also alkali metal bicarbon
  • alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate, calcium carbonate, cesium carbonate and rubidium carbonate.
  • the bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.
  • the starting materials are generally reacted with one another in equimolar amounts.
  • the hydrogenation takes place by reaction with hydrogen in the presence of transition metal catalysts, for example catalysts comprising Pt, Pd, Rh or Ru as active metal species.
  • transition metal catalysts for example catalysts comprising Pt, Pd, Rh or Ru as active metal species.
  • Suitable are both heterogeneous catalysts, such as supported Pd or Pt catalysts, for example Pd on activated carbon, furthermore Pt02, and also homogeneous catalysts.
  • stereoselective catalysts permits an enantioselective hydrogenation of the double bond [cf.: Peptide Chemistry 17, 1980, pp. 59-64; Tetrahedron Lett. 46, 1979, pp. 4483-4486].
  • Compounds of the formula I in which W is N and U is C-R c (formula I. II) can be prepared, for example, from compounds of the formula IVb.
  • This reaction is usually carried out at temperatures of from -78°C to 100°C, preferably from 10°C to 50°C, in an inert organic solvent in the presence of an acid or a Lewis acid or a catalyst, such as, for example, 0.5 N HCI in water/THF (cf.: Helv. Chim. Acta 1986, 69(8), 1887-97).
  • an acid or a Lewis acid or a catalyst such as, for example, 0.5 N HCI in water/THF (cf.: Helv. Chim. Acta 1986, 69(8), 1887-97).
  • Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and
  • chlorobenzene ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and THF, nitriles, such as acetonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, water, and also DMSO, DMF and DMA. It is also possible to use mixtures of the solvents mentioned.
  • ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and THF
  • nitriles such as acetonitrile and propionitrile
  • ketones
  • Suitable for use as acids and acidic catalysts are inorganic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, Lewis acids, such as boron trifluoride, aluminum trichloride, iron(lll) chloride, tin(IV) chloride, titanium(IV) chloride and zinc(ll) chloride, Lewis-acidic solids, such as zeolites, silicates, and also organic acids, such as formic acid, acetic acid, propionic acid, oxalic acid, toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid and trifluoroacetic acid.
  • Lewis acids such as boron trifluoride, aluminum trichloride, iron(lll) chloride, tin(IV) chloride, titanium(IV) chloride and zinc(ll) chloride
  • Lewis-acidic solids such as zeolites, silicates
  • the cyclization of the compounds of the formula IVd to the unsaturated compounds I _ 11 ' can be carried out in the presence of ammonia analogously to the conditions illustrated furth 8].
  • This reaction is carried out in the presence of a hydrazine, usually at temperatures of from 0°C to 180°C, preferably from 50°C to 130°C, in an inert organic solvent [cf.: Eur. J. Med. Chem. 2009, 44, 954-958].
  • Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, nitriles, ketones, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and also DMSO, DMF and DMA, particularly preferably n-propanol and n-butanol. It is also possible to use mixtures of the solvents mentioned.
  • Suitable hydrazines are, in particular, formylhydrazine, acetylhydrazine.
  • the starting materials are generally reacted with one another in equimolar amounts.
  • This reaction is carried out in the presence of an azide, usually at temperatures of from 0°C to 180°C, preferably from 50°C to 130°C, in an inert organic solvent [cf.: Indian J. Chem. 2003, 42B, 256].
  • Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, nitriles, ketones, alcohols, such as methanol, ethanol, n- propanol, isopropanol, n-butanol and tert-butanol, and also DMSO, DMF and DMA, particularly preferably n-propanol and n-butanol. It is also possible to use mixtures of the solvents mentioned.
  • Suitable azides are, in general, alkaline earth metal or alkali metal azides, such as sodium azide, and tosyl azide.
  • the starting materials are generally reacted with one another in equimolar amounts.
  • the unsaturated compounds of the formula ⁇ obtainable by routes illustrated further above can be hydrogenated to given compounds of the formula I" .
  • the hydrogenation takes place by reaction with hydrogen in the presence of transition metal catalysts, for example catalysts comprising Pt, Pd, Rh or Ru as active metal species.
  • transition metal catalysts for example catalysts comprising Pt, Pd, Rh or Ru as active metal species.
  • Suitable are both heterogeneous catalysts, such as supported Pd or Pt catalysts, for example Pd on activated carbon, furthermore Pt02, and also homogeneous catalysts.
  • stereoselective catalysts permits an enantioselective hydrogenation of the double bond [cf.: Peptide Chemistry 17, 1980, pp. 59-64; Tetrahedron Lett. 46, 1979, pp. 4483-4486].
  • reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, chromatographic purification of the crude products.
  • Some of the intermediates and end products are obtained in the form of colorless or slightly brownish viscous oils which are purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, the purification can also be carried out by recrystallization or digestion.
  • organic moieties mentioned for the substituents of the compounds according to the invention are collective terms for individual enumerations of the individual group members.
  • halogenated substituents preferably carry one to five identical or different halogen atoms, in particular fluorine atoms or chlorine atoms.
  • halogen denotes in each case fluorine, chlorine, bromine or iodine.
  • alkyl and the alkyl moieties for example in alkoxy, alkylamino, dialkylamino, N-alkyl- sulfonylamino, alkylaminosulfonylamino, dialkylaminosulfonylamino, N-(alkenyl)-N-
  • alkyl denotes relatively large alkyl groups, such as Cs-Ce-alkyl.
  • Haloalkyl an alkyl radical as mentioned above, some or all of whose hydrogen atoms are substituted by halogen atoms, such as fluorine, chlorine, bromine and/or iodine, for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoro- methyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoro- ethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropy
  • Cycloalkyl and the cycloalkyl moieties for example in cycloalkoxy or
  • cycloalkylcarbonyl monocyclic saturated hydrocarbon groups having three or more carbon atoms, for example 3 to 6 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • Alkenyl and the alkenyl moieties for example in alkenylamino, alkenyloxy,
  • N-(alkenyl)-N-(alkyl)amino, N-(alkenyl)-N-(alkoxy)amino monounsaturated straight- chain or branched hydrocarbon radicals having two or more carbon atoms, for example 2 to 4, 2 to 6 or 3 to 6 carbon atoms, and a double bond in any position, for example C2-C6-alkenyl, such as ethenyl, 1 -propenyl, 2-propenyl, 1 -methylethenyl, 1 -butenyl,
  • Cycloalkenyl monocyclic monounsaturated hydrocarbon groups having 3 to 6, preferably 5 or 6, carbon ring members, such as cyclopenten-1 -yl, cyclopenten-3-yl, cyclohexen-1 -yl, cyclohexen-3-yl, cyclohexen-4-yl.
  • Alkynyl and the alkynyl moieties for example in alkynyloxy, alkynylamino, N-(alkynyl)- N-(alkyl)amino or N-(alkynyl)-N-(alkoxy)amino: straight-chain or branched hydrocarbon groups having two or more carbon atoms, for example 2 to 4, 2 to 6 or 3 to 6 carbon atoms, and a triple bond in any position, for example C2-C6-alkynyl, such as ethynyl,
  • Alkoxy alkyl as defined above which is attached via an oxygen atom, for example methoxy, ethoxy, n-propoxy, 1 -methylethoxy, butoxy, 1 -methylpropoxy, 2-methyl- propoxy or 1 ,1 -dimethylethoxy, pentoxy, 1 -methylbutoxy, 2-methylbutoxy, 3-methyl- butoxy, 1 ,1 -dimethylpropoxy, 1 ,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1 -ethyl- propoxy, hexoxy, 1 -methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methyl- pentoxy, 1 ,1 -dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3-dimethylbutoxy, 2,2-dimethyl- butoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1 -ethylbutoxy, 2-ethylbutoxy,
  • 3- to 7-membered monocyclic or 9- or 10-membered bicyclic saturated, unsaturated or aromatic heterocycle which contains 1 , 2, 3, or 4 heteroatoms selected from the group consisting of O, N and S and which can be attached via C or N.
  • Preferred from among these are 5- or 6-membered heterocycles.
  • Saturated or unsaturated heterocyclic groups which are attached via N such as: pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl,
  • Heteroaromatic groups which are attached via C such as: pyrazol-3-yl, imidazol-5-yl, oxazol-2-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyridazin-4-yl, pyrazin-2-yl, [1 H]-tetrazol-5- yl and [2H]-tetrazol-5-yl.
  • the compounds of the formula I may, depending on the substitution pattern, contain one or more further centers of chirality. Accordingly, the compounds according to the invention can be present as pure enantiomers or diastereomers or as enantiomer or diastereomer mixtures. The invention provides both the pure enantiomers or diastereomers and their mixtures.
  • the compounds of the formula I may also be present in the form of the N-oxides and/or of their agriculturally useful salts, the type of salt generally not being important.
  • Suitable salts are generally the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the herbicidal activity of the compounds I.
  • Suitable cations are in particular ions of the alkali metals, preferably lithium, sodium or potassium, of the alkaline earth metals, preferably calcium or magnesium, and of the transition metals, preferably manganese, copper, zinc or iron.
  • Another cation that may be used is ammonium, where, if desired, one to four hydrogen atoms may be replaced by Ci-C4-alkyl, hydroxy-Ci-C4-alkyl, Ci-C4-alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy- Ci-C4-alkyl, phenyl or benzyl, preferably ammonium, dimethylammonium, diisopropyl- ammonium, tetramethylammonium, tetrabutylammonium, 2-(2-hydroxyeth-1 -oxy)eth-1 - ylammonium, di(2-hydroxyeth-1 -yl)ammonium, trimethylbenzylammonium.
  • ammonium cation is the pyridine nitrogen atom of the formula I quaternized by alkylation or arylation.
  • phosphonium ions preferably tri(Ci-C4-alkyl)sulfonium, or sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium.
  • Anions of suitable acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and also the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate, butyrate or trifluoroacetate.
  • the particularly preferred embodiments of the intermediates correspond to those of the groups of the formula I .
  • variables of the compounds of the formula I have the following meanings, these meanings, both on their own and in combination with one another, being particular embodiments of the compounds of the formula I :
  • W and U are C-R c , where R c is preferably hydroge
  • W is N and U is C-R c where R c is preferably hydroge
  • U is N and W is C-R c where R c is preferably hydrogen.
  • W and U are N.
  • the two groups R 3 and R 4 together are a double bond.
  • the groups R 3 and R 4 are groups R c , in particular hydrogen.
  • A is N and E, G, M, W and U are C-R c , and R 3 and R 4 are together a double bond.
  • R c1 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H
  • R c2 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyi, in particular H;
  • R c3 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyi, in particular H;
  • R c4 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyi, in particular H, Br, OH and OCH 3 ;
  • R c5 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyi, in particular H.
  • a and M are N and E, G, W and U are C-R c , and the two groups R together are a double bond.
  • R c1 is H, OH, CN, halogen, alkyl, alkoxy, haolalkyl, in particular H;
  • R c2 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyi, in particular H;
  • R c3 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyi, in particular H;
  • R c4 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyi, in particular H, Br, OH and OCH 3 .
  • a and M are N and E, G, W and U are C-R c , and R 3 and R 4 together are a double bond. These compounds correspond to the formula 1.3
  • R c1 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyi, in particular H;
  • R c2 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyi, in particular H;
  • R c3 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyi, in particular H, Br, OH and OCH 3
  • R c4 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyi, in particular H, Br, OH and OCH 3 .
  • a and E are N and B, M, W and U are C-R c , and R 3 and R 4 together are a double bond.
  • R c1 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
  • R c2 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
  • R c3 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
  • R c4 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H, Br, OH and OCH 3 .
  • A, E and G are C-R c and M, W and U are N, and R 3 and R 4 together are a double bond.
  • R c1 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
  • R c2 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
  • R c3 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H, Br, OH and OCH 3 ;
  • R c4 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
  • R c5 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H.
  • A is N and E, G, M, W and U are C-R c , and R 3 and R 4 are hydrogen. These compounds correspond to the formula 1.6
  • R c1 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
  • R c2 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
  • R c3 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
  • R c4 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H, Br, OH and OCH 3 ;
  • R c5 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H.
  • a and U are N and E, G, M and W are C-R c , and R 3 and R 4 together are a double bond.
  • R c1 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
  • R c2 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
  • R c3 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H, Br, OH and OCH 3 ;
  • R c4 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H.
  • A, W and U are N and E, G and M are C-R c , and R 3 and R 4 together are a double bond.
  • R c1 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
  • R c2 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H, Br, OH and OCH 3 ;
  • R c3 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H.
  • a and W are N and E, G, M and U are C-R c , and R 3 and R 4 together are a double bond.
  • R c1 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
  • R c2 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
  • R c3 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H, Br, OH and OCH 3 ;
  • R c4 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H.
  • Particularly preferred aspects of the compounds of the formula I relate to those of each of the formulae 1.1 to 1.9 in which the variables have the meanings preferred for formula I.
  • R 1 is 0-R A .
  • R 1 is S(0) n -R A where n is preferably 0 or 2, in particular 2.
  • R 1 is 0-S(0) n -R A , where n is preferably 0 or 2, in particular 2, such as, for example, OS(0) 2 -CH 3 , OS(0) 2 -C 2 H 5 , OS(0) 2 -C 3 H 7 , OS(0) 2 - C 6 H 5 or OS(0) 2 -(4-CH 3 -C 6 H 4 ).
  • R 1 is 0-S(0) n -NR'R ii , which has in particular the groups NR'R" mentioned below as being preferred.
  • R A is in particular H, Ci-C 6 -alkylcarbonyl, such as C(0)CH 3 , C(0)CH 2 CH 3 ,
  • Ci-C6-cycloalkylcarbonyl such as cyclopropylcarbonyl, cyclopentylcarbonyl or cyclohexylcarbonyl
  • C 2 -C6-alkenylcarbonyl such as
  • R A is H or Ci-C6-alkylcarbonyl.
  • R A is selected from the group consisting of H, OCH 3 , C(0)CH 3 , C(0)CH 2 CH 3 , C(0)CH(CH 3 ) 2 , C(0)C(CH 3 ) 3 , C(0)-c-C 3 H 5 , C(0)-C 6 H 5 , C(O)- CH 2 C 6 H 5 , C(0)CH 2 CI, C(0)CF 3 , C(0)CH 2 OCH 3 , C(0)N(CH 3 ) 2 and C(0)OCH 2 CH 3 .
  • R A is NR'R".
  • R A is Z-NR'-C(0)-NR'R'', where R' and R" are as defined at the outset and preferably as defined below.
  • Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy and Ci-C 4 -alkoxy-Ci-C 4 -alkyl in particular OCH 3 , OC 2 H 5 , CH 2 CH 2 OCH 3 and CH 2 CH 2 CI, may also be possible for R' and R", independently of one another.
  • Particularly preferred aspects of the group NR'R" are N(di-Ci-C 4 -alkyl), in particular N(CH 3 )-Ci-C 4 -alkyl, such as N(CH 3 ) 2 ,
  • NR'R" are NH-aryl, where aryl is preferably phenyl which is substituted - in particular in the 2- and 6-position - by one to three identical or different halogen, CH 3 , halo-Ci-C2-alkyl, halo-Ci-C2-alkoxy and carboxyl groups, such as 2-CI-6-COOH-C 6 H 3 , 2,6-CI 2 -C 6 H 3 , 2,6-F 2 -C 6 H 3 , 2,6-CI 2 -3-CH 3 -C 6 H 2 , 2- CF 3 -6-CH 2 CHF 2 -C 6 H 3 , 2-CF 3 -6-OCF 3 -C 6 H 3 and 2-CF 3 -6-CH 2 CHF 2 -C 6 H 3 .
  • aryl is preferably phenyl which is substituted - in particular in the 2- and 6-position - by one to three identical or different halogen, CH 3 , halo-Ci-C2-alkyl
  • NR'R are NH-heteroaryl, where heteroaryl is preferably one of the preferred heteroaromatic groups below, in particular triazinyl, pyrimidinyl or
  • triazolopyrimidinyl such as [1 ,2,4]triazolo[1 ,5-a]pyrimidin-2-yl, which groups may be substituted, in particular by Ci-C 4 -alkoxy and/or halogen.
  • R 1 is selected from the group consisting of OH, OCH 3 , OC(0)CH 3 , OC(0)CH 2 CH 3 , OC(0)CH(CH 3 ) 2 , OC(0)C(CH 3 ) 3 , OC(0)-c-C 3 H 5 , OC(0)-C 6 H 5 , OC(0)-CH 2 C 6 H 5 , OC(0)CH 2 CI, OC(0)-CF 3 , OC(0)-CH 2 OCH 3 , OC(O)- N(CH 3 ) 2 and OC(0)-OCH 2 CH 3 .
  • R 2 is phenyl which is substituted by a group selected from the group consisting of 2-Br, 2-CI, 2,4-CI 2 , 2-CI-4-F, 2-CI-5-F, 2-CI-6-F, 2-CI-4- CF 3 , 2-CI-5-CF 3 , 2-CI-6-CF 3 , 2-CI-3,6-F 2 , 2-F, 2,4-F 2 , 2,5-F 2 , 2,6-F 2 , 2-F-4-CF 3 , 2-F-5- CF 3 , 2-F-6-CF 3 , 2,3,6-F 3 , 2-N0 2 , 2-N0 2 -4-F, 2-N0 2 -5-F, 2-N0 2 -6-F, 2-N0 2 -4-CF 3 , 2- N0 2 -5-CF 3 , 2-N0 2 -6-CF 3 , 2-N0 2 -3,6-F 2 , 2-CN, 2-CH 3 , 2-N0 2 -5-CF 3 , 2-N0 2 -6-CF 3
  • R A is a 5- or 6-membered heterocycle optionally substituted by R b as defined above, which preferably has either 1 , 2, 3 or 4 nitrogen atoms or 1 oxygen or 1 sulfur atom and if appropriate 1 or 2 nitrogen atoms as ring members and which is unsubstituted or may have 1 or 2 substituents selected from R b .
  • Heteroaromatic groups pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, pyrazol-1 -yl, pyrazol-3- yl, pyrazol-4-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, imidazol-1 -yl, imidazol-2-yl, imidazol-4-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl and thi
  • R A is a heteroaromatic group attached via carbon, such as pyrazol- 3-yl, imidazol-5-yl, oxazol-2-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, pyridin-2-yl, pyridin- 3-yl, pyridin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyridazin-4-yl, pyrazin-2- yl, [1 H]-tetrazol-5-yl and [2H]-tetrazol-5-yl, where each of the heterocycles mentioned here in an exemplary manner may have 1 or 2 substituents selected from R b .
  • Preferred groups R b are in particular F, CI, CN, N0 2 , CH 3 , C 2 H 5 , OCH 3 , OC 2 H 5 ,
  • R 2 is phenyl which is unsubstituted or partially or fully substituted by groups R b .
  • Particular preference is given to compounds in which a group R b is located in the ortho-position.
  • Such compounds of the formula I are described by the formula I.
  • the index m is zero or an integer from one to four, preferably 0, 1 or 2, in particular 0 or 1.
  • R 5 and R 6 are groups R b as defined at the outset, preferably halogen, NO2, Ci-C4-alkyl, Ci-C2-haloalkyl and Ci-C4-alkoxy.
  • One group R 6 is preferably located in position 5.
  • a group R 6 in position 3 is a further preferred embodiment.
  • R 5 is Br, F, N0 2 , CN, CH 3 , OCH 3 , CF 3 , OCF 3 , CHF 2 or OCHF2.
  • R 6 is particularly preferably halogen or halomethyl, such as CI, F or CF3.
  • (R 6 ) m is selected from the group consisting of 4-F, 5-F, 5-CI, 6-F, 4-CFs, 5-CFs and 3,6-F 2 .
  • phenyl such as C 6 H 5 , 4-CH3-C 6 H 4 , 4-F-C 6 H 4 or S(0) n -R N , where R N is Ci-C 6 -haloalkyl, such as CH2CF3,
  • R c is preferably ⁇ , ⁇ , CN, halogen, alkyl, alkoxy, haloalkyl, in particular H.
  • a further embodiment relates to the N-oxides of the compounds of the formula I.
  • a further embodiment relates to salts of the compounds of the formula I, in particular those which are obtainable by quaternization of the pyridine nitrogen atom, which may preferably take place by alkylation or arylation of the compounds of the formula I.
  • Preferred salts of the compounds are thus the N-alkyl salts, in particular the N-methyl salts, and the N-phenyl salts.
  • T1 NH(4-CH 3 -C 6 H 4 )
  • T2 N(CH 3 ) 2
  • T3 N(CH 3 )CH 2 CH 3
  • T4 N(CH 3 )C 3 H 7
  • T5 N(CH 3 )CH(CH 3 ) 2
  • T6 NH(2-CI-6-COOH-C 6 H 3 )
  • T7 NH(2,6-CI 2 -C 6 H 3 )
  • T8 NH(2,6-F 2 -C 6 H 3 )
  • T9 NH(2,6-CI 2 -3-CH 3 -C 6 H 2 )
  • T10 : NH(2-CF 3 -6-CH 2 CHF 2 -C6H 3 )
  • T1 1 : NH(2-CF3-6-OCF3-C 6 H 3 )
  • T12 : NH(2-CF 3 -6-OCH 2 CHF 2 -C6H 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. They are suitable as such or as an appropriately formulated composition.
  • the compounds I in particular the preferred aspects thereof, or compositions comprising them can additionally be employed in a further number of crop plants for eliminating unwanted plants.
  • suitable crops are the following:
  • crop plants also includes plants which have been modified by breeding, mutagenesis or genetic engineering. Genetically modified plants are plants whose genetic material has been modified in a manner which does not occur under natural conditions by crossing, mutations or natural recombination (i.e. reassembly of the genetic information).
  • genetically modified plants are plants whose genetic material has been modified in a manner which does not occur under natural conditions by crossing, mutations or natural recombination (i.e. reassembly of the genetic information).
  • one or more genes are integrated into the genetic material of the plant to improve the properties of the plant.
  • crop plants also includes plants which, by breeding and genetic engineering, have acquired tolerance to certain classes of herbicides, such as hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, acetolactate synthase (ALS) inhibitors, such as, for example, sulfonylureas (EP-A-0257993, US 5,013,659) or imidazolinones (see, for example, US 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673,
  • herbicides such as hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, acetolactate synthase (ALS) inhibitors, such as, for example, sulfonylureas (EP-A-0257993, US 5,013,659) or imidazolinones
  • EPSPS enolpyruvylshikimate 3-phosphate synthase
  • EPSPS enolpyruvylshikimate 3-phosphate synthase
  • GS glutamine synthetase
  • glufosinate see, for example, EP-A-0242236, EP-A-242246, or oxynil herbicides (see, for example, US 5,559,024).
  • imidazolinones for example imazamox
  • mutagenesis Crop plants such as soybeans, cotton, corn, beet and oilseed rape, resistant to glyphosate or glufosinate, which are available under the tradenames RoundupReady ® (glyphosate) and Liberty Link ® (glufosinate) have been generated with the aid of genetic engineering methods.
  • crop plants also includes plants which, with the aid of genetic engineering, produce one or more toxins, for example those of the bacterial strain Bacillus ssp.
  • Toxins which are produced by such genetically modified plants include, for example, insecticidal proteins of Bacillus spp., in particular B.
  • thuringiensis such as the endotoxins Cry1 Ab, Cry1 Ac, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 , Cry9c, Cry34Ab1 or Cry35Ab1 ; or vegetative insecticidal proteins (VIPs), for example VIP1 , VIP2, VIP3, or VIP3A; insecticidal proteins of nematode-colonizing bacteria, for example Photorhabdus spp. or Xenorhabdus spp.; toxins of animal organisms, for example wasp, spider or scorpion toxins; fungal toxins, for example from
  • Streptomycetes ; plant lectins, for example from peas or barley; agglutinins; proteinase inhibitors, for example trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors, ribosome-inactivating proteins (RIPs), for example ricin, corn-RIP, abrin, luffin, saporin or bryodin; steroid-metabolizing enzymes, for example 3- hydroxysteroid oxidase, ecdysteroid-IDP glycosyl transferase, cholesterol oxidase, ecdysone inhibitors, or HMG-CoA reductase; ion channel blockers, for example inhibitors of sodium channels or calcium channels; juvenile hormone esterase;
  • proteinase inhibitors for example trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors, ribosome-inactivating proteins (RIPs
  • these toxins may also be produced as pretoxins, hybrid proteins or truncated or otherwise modified proteins. Hybrid proteins are characterized by a novel combination of different protein domains (see, for example, WO 2002/015701 ). Further examples of such toxins or genetically modified plants which produce these toxins are disclosed in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/018810 and WO 03/052073.
  • crop plants also includes plants which, with the aid of genetic engineering, produce one or more proteins which are more robust or have increased resistance to bacterial, viral or fungal pathogens, such as, for example, pathogenesis- related proteins (PR proteins, see EP-A 0 392 225), resistance proteins (for example potato varieties producing two resistance genes against Phytophthora infestans from the wild Mexican potato Solanum bulbocastanum) or T4 lysozyme (for example potato cultivars which, by producing this protein, are resistant to bacteria such as Erwinia amylvora).
  • PR proteins pathogenesis- related proteins
  • resistance proteins for example potato varieties producing two resistance genes against Phytophthora infestans from the wild Mexican potato Solanum bulbocastanum
  • T4 lysozyme for example potato cultivars which, by producing this protein, are resistant to bacteria such as Erwinia amylvora.
  • crop plants also includes plants whose productivity has been improved with the aid of genetic engineering methods, for example by enhancing the potential yield (for example biomass, grain yield, starch, oil or protein content), tolerance to drought, salt or other limiting environmental factors or resistance to pests and fungal, bacterial and viral pathogens.
  • potential yield for example biomass, grain yield, starch, oil or protein content
  • tolerance to drought for example drought, salt or other limiting environmental factors or resistance to pests and fungal, bacterial and viral pathogens.
  • crop plants also includes plants whose ingredients have been modified with the aid of genetic engineering methods in particular for improving human or animal diet, for example by oil plants producing health-promoting long-chain omega 3 fatty acids or monounsaturated omega 9 fatty acids (for example Nexera ® oilseed rape).
  • crop plants also includes plants which have been modified with the aid of genetic engineering methods for improving the production of raw materials, for example by increasing the amylopectin content of potatoes (Amflora ® potato).
  • the compounds of the formula I are also suitable for the defoliation and/or desiccation of plant parts, for which crop plants such as cotton, potato, oilseed rape, sunflower, soybean or field beans, in particular cotton, are suitable.
  • crop plants such as cotton, potato, oilseed rape, sunflower, soybean or field beans, in particular cotton
  • compositions for the desiccation and/or defoliation of plants processes for preparing these compositions and methods for desiccating and/or defoliating plants using the compounds of the formula I.
  • the compounds of the formula I are particularly suitable for desiccating the above-ground parts of crop plants such as potato, oilseed rape, sunflower and soybean, but also cereals. This makes possible the fully mechanical harvesting of these important crop plants.
  • Also of economic interest is to facilitate harvesting, which is made possible by concentrating within a certain period of time the dehiscence, or reduction of adhesion to the tree, in citrus fruit, olives and other species and varieties of pomaceous fruit, stone fruit and nuts.
  • the same mechanism i.e. the promotion of the development of abscission tissue between fruit part or leaf part and shoot part of the plants is also essential for the readily controllable defoliation of useful plants, in particular cotton.
  • the compounds I, or the herbicidal compositions comprising the compounds I can be used, for example, in the form of ready-to-spray aqueous solutions, powders, suspensions, also highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for broadcasting, or granules, by means of spraying, atomizing, dusting, spreading, watering or treatment of the seed or mixing with the seed.
  • the use forms depend on the intended purpose; in each case, they should ensure the finest possible distribution of the active ingredients 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 which are customary for the formulation of crop protection agents.
  • auxiliaries customary for the formulation of crop protection agents are inert auxiliaries, solid carriers, surfactants (such as dispersants, protective colloids, emulsifiers, wetting agents and tackifiers), organic and inorganic thickeners, bactericides, antifreeze agents, antifoams, if appropriate colorants and, for seed formulations, adhesives.
  • thickeners i.e. compounds which impart to the formulation modified flow properties, i.e. high viscosity in the state of rest and low viscosity in motion
  • thickeners i.e. compounds which impart to the formulation modified flow properties, i.e. high viscosity in the state of rest and low viscosity in motion
  • thickeners i.e. compounds which impart to the formulation modified flow properties, i.e. high viscosity in the state of rest and low viscosity in motion
  • polysaccharides such as xanthan gum (Kelzan® from Kelco), Rhodopol® 23
  • antifoams examples include silicone emulsions (such as, for example, Silikon ® SRE, Wacker or Rhodorsil® from Rhodia), long-chain alcohols, fatty acids, salts of fatty acids, organofluorine compounds and mixtures thereof.
  • Bactericides can be added for stabilizing the aqueous herbicidal formulation.
  • bactericides examples include bactericides based on diclorophen and benzyl alcohol hemiformal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas), and also isothiazolinone derivates, such as alkylisothiazolinones and benzisothiazolinones (Acticide MBS from Thor Chemie).
  • antifreeze agents are ethylene glycol, propylene glycol, urea or glycerol.
  • colorants are both sparingly water-soluble pigments and water-soluble dyes. Examples which may be mentioned are the dyes known under the names Rhodamin B, C.I. Pigment Red 1 12 and C.I.
  • Solvent Red 1 and also pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 1 12, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
  • adhesives are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose.
  • Suitable inert auxiliaries are, for example, the following:
  • mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, for example amines such as N-methyl- pyrrolidone, and water.
  • paraffin tetrahydronaphthalene
  • alkylated naphthalenes and their derivatives alkylated benzenes and their derivatives
  • alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol
  • ketones such as cyclohexanone or strongly
  • Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate and magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate and ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders, or other solid carriers.
  • mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate and magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate and urea
  • Suitable surfactants are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, for example lignosulfonic acids (e.g.
  • methylcellulose methylcellulose
  • hydrophobically modified starches polyvinyl alcohol (Mowiol types Clariant), polycarboxylates (BASF SE, Sokalan types), polyalkoxylates, polyvinylamine (BASF SE, Lupamine types), polyethyleneimine (BASF SE, Lupasol types), polyvinylpyrrolidone and copolymers thereof.
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active ingredients 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.
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • emulsions, pastes or oil dispersions the compounds of the formula I or la, either as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetting agent, tackifier, dispersant or emulsifier.
  • concentrates comprising active substance, wetting agent, tackifier, dispersant or emulsifier and, if desired, solvent or oil, which are suitable for dilution with water.
  • the formulations comprise from 0.001 to 98% by weight, preferably 0.01 to 95% by weight of at least one active compound.
  • the active compounds are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
  • the compounds I of the invention can for example be formulated as follows:
  • active compound 10 parts by weight of active compound are dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other adjuvants are added. The active compound dissolves upon dilution with water. This gives a formulation with an active compound content of 10% by weight.
  • active compound 20 parts by weight of active compound are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion.
  • a dispersant for example polyvinylpyrrolidone.
  • the active compound content is 20% by weight.
  • active compound 15 parts by weight of active compound are dissolved in 75 parts by weight of an organic solvent (e.g. alkylaromatics) with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion.
  • the formulation has an active compound content of 15% by weight.
  • active compound 25 parts by weight of active compound are dissolved in 35 parts by weight of an organic solvent (e.g. alkylaromatics) with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight).
  • organic solvent e.g. alkylaromatics
  • calcium dodecylbenzenesulfonate and castor oil ethoxylate in each case 5 parts by weight.
  • This mixture is introduced into 30 parts by weight of water by means of an emulsifier (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion.
  • emulsifier e.g. Ultraturrax
  • active compound 20 parts by weight of active compound are comminuted with addition of 10 parts by weight of dispersants and wetters and 70 parts by weight of water or an organic solvent to give a fine active compound suspension. Dilution with water gives a stable suspension of the active compound.
  • the active compound content in the formulation is 20% by weight.
  • active compound 50 parts by weight of active compound are ground finely with addition of 50 parts by weight of dispersants and wetters and made into water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound.
  • the formulation has an active compound content of 50% by weight.
  • active compound 75 parts by weight of active compound are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound.
  • the active compound content of the formulation is 75% by weight.
  • the compounds I or the herbicidal compositions comprising them can be applied pre- or post-emergence, or together with the seed of a crop plant. It is also possible to apply the herbicidal compositions or active compounds by applying seed, pretreated with the herbicidal compositions or active compounds, of a crop plant. If the active compounds are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of the spraying equipment, in such a way that as far as possible they do not come into contact with the leaves of the sensitive crop plants, while the active compounds reach the leaves of undesirable plants growing underneath, or the bare soil surface (post-directed, lay-by).
  • the compounds of the formula I or the herbicidal compositions can be applied by treating seed.
  • the treatment of seed comprises essentially all procedures familiar to the person skilled in the art (seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping and seed pelleting) based on the compounds of the formula I according to the invention or the compositions prepared therefrom.
  • the herbicidal compositions can be applied diluted or undiluted.
  • seed comprises seed of all types, such as, for example, corns, seeds, fruits, tubers, cuttings and similar forms.
  • seed describes corns and seeds.
  • the seed used can be seed of the useful plants mentioned above, but also the seed of transgenic plants or plants obtained by customary breeding methods.
  • the rates of application of active compound are from 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 compounds I are generally employed in amounts of from 0.001 to 10 kg per 100 kg of seed.
  • Safeners are chemical compounds which prevent or reduce damage to useful plants without substantially affecting the herbicidal action of the compounds of the formula I on unwanted plants. They can be used both before sowing (for example in the treatment of seed, or on cuttings or seedlings) and before or after the emergence of the useful plant.
  • the safeners and the compounds of the formula I can be used simultaneously or in succession.
  • Suitable safeners are, for example, (quinolin-8- oxy)acetic acids, 1 -phenyl-5-haloalkyl-1 H-1 ,2,4-triazole-3-carboxylic acids, 1 -phenyl- 4,5-dihydro-5-alkyl-1 H-pyrazole-3,5-dicarboxylic acids, 4,5-dihydro-5,5-diaryl-3- isoxazolecarboxylic acids, dichloroacetamides, alpha-oximinophenylacetonitriles, acetophenone oximes, 4,6-dihalo-2-phenylpyrimidines, N-[[4-(aminocarbonyl)phenyl]- sulfonyl]-2-benzamides, 1 ,8-naphthalic anhydride, 2-halo-4-(haloalkyl)-5-thiazole- carboxylic acids, phosphorothiolates and O-phenyl N-alkyl
  • the compounds of the formula I can be mixed and jointly applied with numerous representatives of other herbicidal or growth-regulating groups of active compounds or with safeners.
  • Suitable mixing partners are, for example, 1 ,2,4-thiadiazoles, 1 ,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anilides, aryloxy/heteroaryl- oxyalkanoic acids and their derivatives, benzoic acid and its derivatives,
  • benzothiadiazinones 2-(hetaroyl/aroyl)-1 ,3-cyclohexanediones, heteroaryl aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinoline carboxylic acid and its derivatives, chloroacetanilides, cyclohexenone oxime ether derivates, diazines, dichloropropionic acid and its derivatives, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- and heteroaryl
  • herbicides which can be used in combination with the pyridine compounds of the formula I according to the present invention are:
  • ametryn amicarbazone, atrazine, bentazone, bentazone-sodium, bromacil, bromofenoxim, bromoxynil and its salts and esters, chlorobromuron, chloridazone, chlorotoluron, chloroxuron, cyanazine, desmedipham, desmetryn, dimefuron, dimethametryn, diquat, diquat-dibromide, diuron, fluometuron, hexazinone, ioxynil and its salts and esters, isoproturon, isouron, karbutilate, lenacil, linuron, metamitron, methabenzthiazuron, metobenzuron, metoxuron, metribuzin, monolinuron, neburon, paraquat, paraquat-dichloride, paraquat-dimetilsulfate, pentanochlor, phenmedipham, phenmedipham-e
  • acifluorfen acifluorfen-sodium, azafenidin, bencarbazone, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, cinidon-ethyl, fluazolate, flufenpyr, flufenpyr-ethyl, flumiclorac, flumiclorac-pentyl, flumioxazin, fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen, pyraflufen-ethyl, saflufenacil, sulfentrazone,
  • diflufenican fluridone, flurochloridone, flurtamone, isoxaflutole, mesotrione,
  • bilanaphos (bialaphos), bilanaphos-sodium, glufosinate and glufosinate-ammonium; b8) from the group of the DHP synthase inhibitors:
  • amiprophos amiprophos-methyl, benfluralin, butamiphos, butralin, carbetamide, chlorpropham, chlorthal, chlorthal-dimethyl, dinitramine, dithiopyr, ethalfluralin, fluchloralin, oryzalin, pendimethalin, prodiamine, propham, propyzamide, tebutam, thiazopyr and trifluralin;
  • acetochlor alachlor, anilofos, butachlor, cafenstrole, dimethachlor, dimethanamid, dimethenamid-P, diphenamid, fentrazamide, flufenacet, mefenacet, metazachlor, metolachlor, metolachlor-S, naproanilide, napropamide, pethoxamid, piperophos, pretilachlor, propachlor, propisochlor, pyroxasulfone (KIH-485) and thenylchlor;
  • Y is phenyl or 5- or 6-membered heteroaryl as defined at the outset, which radicals may be substituted by one to three groups R aa ; R 21 ,R 22 ,R 23 ,R 24 are H, halogen or Ci-C 4 -alkyl; X is O or NH; N is 0 or 1 .
  • R2i i R 22 R 23 R 24 are H i C!i F or CH 3 ;
  • R 25 is halogen, Ci-C 4 -alkyl or Ci-C 4 -haloalkyl;
  • R 26 is Ci-C 4 -alkyl;
  • R 27 is halogen, Ci-C 4 -alkoxy or Ci-C 4 -haloalkoxy;
  • R 28 is H, halogen, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl or Ci-C 4 -haloalkoxy;
  • M is 0, 1 , 2 or 3;
  • X is oxygen;
  • N is 0 or 1 .
  • Preferred compounds of the formula 2 have the following meanings:
  • R 21 is H; R 22 ,R 23 are F; R 24 is H or F; X is oxygen; N is 0 or 1 .
  • Particularly preferred compounds of the formula 2 are:
  • auxin transport inhibitors diflufenzopyr, diflufenzopyr- sodium, naptalam and naptalam-sodium;
  • Examples of preferred safeners C are benoxacor, cloquintocet, cyometrinil, cyprosulfamide, dichlormid, dicyclonone, dietholate, fenchlorazole, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen, mefenpyr, mephenate, naphthalic anhydride, oxabetrinil, 4-(dichloroacetyl)-1 -oxa-4-azaspiro[4.5]decane (H-1 1 ; MON4660, CAS 71526-07-3) and 2,2,5-trimethyl-3-(dichloroacetyl)-1 ,3-oxazolidine (H-12; R-29148, CAS 52836-31 -4).
  • the active compounds of groups b1 ) to b15) and the safeners C are known herbicides and safeners, see, for example, The Compendium of Pesticide Common Names (http://www.alanwood.net/pesticides/); B. Hock, C. Fedtke, R. R. Schmidt, Herbizide [Herbicides], Georg Thieme Verlag, Stuttgart, 1995. Further herbicidally active compounds are known from WO 96/26202, WO 97/41 1 16, WO 97/41 1 17, WO 97/41 1 18, WO 01/83459 and WO 2008/074991 and from W. Kramer et al. (ed.) "Modern Crop Protection Compounds", Vol.
  • the invention also relates to compositions in the form of a crop protection composition formulated as a 1 -component composition comprising an active compound combination comprising at least one pyridine compound of the formula I and at least one further active compound, preferably selected from the active compounds of groups b1 to b15, and at least one solid or liquid carrier and/or one or more surfactants and, if desired, one or more further auxiliaries customary for crop protection compositions.
  • the invention also relates to compositions in the form of a crop protection composition formulated as a 2-component composition
  • a first component comprising at least one pyridine compound of the formula I, a solid or liquid carrier and/or one or more surfactants and a second component comprising at least one further active compound selected from the active compounds of groups b1 to b15, a solid or liquid carrier and/or one or more surfactants, where additionally both components may also comprise further auxiliaries customary for crop protection compositions.
  • the weight ratio of the active compounds A:B is generally in the range of from 1 :1000 to 1000:1 , preferably in the range of from 1 :500 to 500:1 , in particular in the range of from 1 :250 to 250:1 and particularly preferably in the range of from 1 :75 to 75:1.
  • the weight ratio of the active compounds A:C is generally in the range of from 1 :1000 to 1000:1 , preferably in the range of from 1 :500 to 500:1 , in particular in the range of from 1 :250 to 250:1 and particularly preferably in the range of from 1 :75 to 75: 1.
  • the relative parts by weight of the components A:B are generally in the range of from 1 :1000 to 1000:1 , preferably in the range of from 1 :500 to 500:1 , in particular in the range of from 1 :250 to 250:1 and particularly preferably in the range of from 1 :75 to 75:1 ;
  • the weight ratio of the components A:C is generally in the range of from 1 :1000 to 1000:1 , preferably in the range of from 1 :500 to 500:1 , in particular in the range of from 1 :250 to 250:1 and particularly preferably in the range of from 1 :75 to 75:1 ;
  • the weight ratio of the components B:C is generally in the range of from 1 :1000 to 1000:1 , preferably in the range of from 1 :500 to 500:1 , in particular in the range of from 1 :250 to 250:1 and particularly preferably in the range of from 1 :75 to 75:1 ;
  • the weight ratio of the components B:C is generally in the range of
  • the weight ratio of the components A + B to the component C is in the range of from 1 :500 to 500:1 , in particular in the range of from 1 :250 to 250:1 and particularly preferably in the range of from 1 :75 to 75:1.
  • the active compounds in the compositions described are in each case preferably present in synergistically effective amounts.
  • the compounds I and the compositions according to the invention may also have a plant-strengthening action. Accordingly, they are suitable for mobilizing the defense system of the plants against attack by unwanted microorganisms, such as harmful fungi, but also viruses and bacteria.
  • Plant-strengthening (resistance-inducing) substances are to be understood as meaning, in the present context, those substances which are capable of stimulating the defense system of treated plants in such a way that, when subsequently inoculated by unwanted microorganisms, the treated plants display a substantial degree of resistance to these microorganisms.
  • the compounds I can be employed for protecting plants against attack by unwanted microorganisms within a certain period of time after the treatment.
  • the period of time within which their protection is effected generally extends from 1 to 28 days, preferably from 1 to 14 days, after the treatment of the plants with the compounds I, or, after treatment of the seed, for up to 9 months after sowing.
  • the compounds I and the compositions according to the invention are also suitable for increasing the harvest yield.

Abstract

L'invention porte sur des composés tricycliques représentés par la formule (I) dans laquelle les variables sont telles que définies dans la description, sur leurs sels de qualité agricole, sur des procédés et des intermédiaires permettant de préparer les composés représentés par la formule (I), sur des compositions les comprenant et sur leur utilisation comme herbicides, c'est-à-dire pour la lutte contre des plantes nuisibles, et également sur un procédé de lutte contre de la végétation non voulue qui consiste à laisser une quantité efficace du point de vue herbicide d'au moins un composé représenté par la formule (I) agir sur des plantes, leur graine et/ou leur habitat.
PCT/EP2010/067176 2009-11-13 2010-11-10 Composés tricycliques ayant un effet herbicide WO2011058036A1 (fr)

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US8440594B2 (en) 2010-03-23 2013-05-14 Basf Se Pyridothiazines having herbicidal action
US8575068B2 (en) 2010-03-23 2013-11-05 Basf Se Pyrazinothiazines having herbicidal action
US8809535B2 (en) 2010-03-23 2014-08-19 Basf Se Substituted pyridines having herbicidal action
US8921273B2 (en) 2010-03-23 2014-12-30 Basf Se Substituted pyridazines having herbicidal action
US10294488B2 (en) 2012-12-18 2019-05-21 Basf Se Herbicide-metabolizing cytochrome P450 monooxygenases

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US8575068B2 (en) 2010-03-23 2013-11-05 Basf Se Pyrazinothiazines having herbicidal action
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US10294488B2 (en) 2012-12-18 2019-05-21 Basf Se Herbicide-metabolizing cytochrome P450 monooxygenases

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