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WO2011058036A1 - Tricyclic compounds having herbicidal action - Google Patents

Tricyclic compounds having herbicidal action 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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Inventor
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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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.

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Abstract

Tricyclic compounds of the formula (I) in which the variables are defined according to the description, their agriculturally suitable salts, processes and intermediates for preparing the compounds of the formula (I), compositions comprising them and their use as herbicides, i.e. for controlling harmful plants, and also a method for controlling unwanted vegetation which comprises allowing a herbicidally effective amount of at least one compound of the formula (I) to act on plants, their seed and/or their habitat.

Description

Tricyclic compounds having herbicidal action Description The present invention relates to tricyclic compounds of the formula I
Figure imgf000003_0001
in which the variables have the following meaning:
R1 is 0-RA, S(0)n-RA or 0-S(0)n-RA;
RA is hydrogen, Ci-C4-alkyl, Z-C3-C6-cycloalkyl, Ci-C4-haloalkyl,
C2-C6-alkenyl, Z-C3-C6-cycloalkenyl, C2-C6-alkynyl,
Z-(tri-Ci-C4-alkyl)silyl, Z-C(=0)-Ra, -NR'-C(0)-NR'R'', Z-P(=0)(Ra)2, NR'R", a 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, which may be partially or fully substituted by groups Ra and/or Rb, Ra is hydrogen, OH, d-Cs-alkyl, Ci-C4-haloalkyl, Z-C3-C6-cycloalkyl, C2-Cs-alkenyl, Z-Cs-Ce-cycloalkenyl, C2-Cs-alkynyl, Z-Ci-C6-alkoxy, Z-Ci-C4-haloalkoxy, Z-Cs-Cs-alkenyloxy, Z-Cs-Cs-alkynyloxy,
NR'R", d-Ce-alkylsulfonyl, Z-(tri-Ci-C4-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,
4 or 5 groups Rb;
R', R" independently of one another are hydrogen, Ci-Cs-alkyl, Ci-C4-haloalkyl, Cs-Cs-alkenyl, Cs-Cs-alkynyl,
Z-C3-C6-cycloalkyl, Z-Ci-Cs-alkoxy, Z-Ci-Cs-haloalkoxy, Z-C(=0)-Rb, Z-phenyl, a 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 is attached via Z;
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 is 0, 1 or 2;
R2 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
unsubstituted or substituted by 1 , 2, 3, 4 or 5 groups Rb;
Rb independently of one another are Z-CN, Z-OH, Z-NO2, Z-halogen,
d-Cs-alkyl, Ci-C4-haloalkyl, C2-C8-alkenyl, C2-C8-alkynyl,
Z-Ci-Cs-alkoxy, Z-d-Cs-haloalkoxy, Z-C3-Cio-cycloalkyl, O-Z-Cs-Cio-cycloalkyl, Z-C(=0)-Rbb, NR'R", Z-(tri-Ci-C4-alkyl)silyl, Z-phenyl and S(0)nRbb, where
Rbb is Ci-Cs-alkyl or Ci-C6-haloalkyl and n is 0, 1 or 2;
Rb together with the group Rb 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-Rc, one or two of these groups being N;
Rc is hydrogen or one of the groups mentioned for Rb;
R3, R4 independently of one another are a group Rc or the two groups together are a double bond;
W, U independently of one another are N and C-Rc;
where in the groups Z, RA, R2, Rc and their subsubstituents, the carbon chains and/or the cyclic groups may be partially or fully substituted by groups Rb,
or an N-oxide or an agriculturally suitable salt thereof.
Moreover, 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.
Further embodiments of the present invention can be found in the claims, the description and the examples. It is to be understood that the features mentioned above and those still to be illustrated below of the subject matter of the invention can be applied not only in the respective given combination but also in other combinations without leaving the scope of the invention.
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.
It is an object of the present invention to provide compounds having herbicidal action. To be provided are in particular active compounds having strong herbicidal action, in particular even at low application rates, whose compatibility with crop plants is sufficient for commercial application.
These and further objects are achieved by the compounds of the formula I defined at the outset and by their N-oxides and also their agriculturally suitable salts.
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-Rc (formula I.I) 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. In the formulae II, III and IV, the variables have the meaning given for formula I. The group R is C1-C6 alkyl, such as, preferably, methyl or ethyl.
Figure imgf000005_0001
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).
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.
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, such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium, moreover organic bases, for example tertiary amines, such as trimethylamine, triethylamine, tributylamine, diisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, hexamethyldisilazane, and also bicyclic amines.
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 Γ in which W and U are C-Rc and R3 and R4 together are a double bond
Figure imgf000006_0001
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].
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.
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.
Alternatively, 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.
Figure imgf000007_0001
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.
Compounds of the formula IVa can also be obtained by alkylation from compounds of the formula II according to standard methods of organic chemistry. In formula Ilia, X1 is a nucleophilic leaving group, such as, for example, halogen, alkyl sulfate or alkylsulfonate.
Figure imgf000007_0002
The keto compounds of the formula IVb can be released from the acetals of the formula IVa.
Figure imgf000008_0001
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].
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.
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.
The cyclization of IVb to compounds of the formula Ι.Γ can be carried out using, for example, ammonia.
Figure imgf000008_0002
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.:
Bioorg. Med. Chem. Lett. 2008, 18, 5605-5608].
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.
A further preparation method for compounds of the formula I proceeds via a 2-halo- pyridine intermediate of the formula IVc. In formula IVc, X is halogen, preferably chlorine or bromine, in particular chlorine.
Figure imgf000009_0001
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 PCI3, PCI5, POCI3, PBr3, PBr5.
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 and alkaline earth metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert- butoxide and dimethoxymagnesium, moreover organic bases, for example tertiary amines, such as trimethylamine, triethylamine, tributylamine, diisopropylethylamine and n-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4- dimethylaminopyridine, and also bicyclic amines. Particular preference is given to amines, such as triethylamine, diisopropylethylamine. 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.
Alternatively, the compounds of the formula IV can also be prepared by reacting co
Figure imgf000010_0001
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.
Particular preference is given to 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.
Compounds of the formula IV can be cyclized as described above to compounds of the formula I.
Compounds of the formula Ι.Γ can be hydrogenated to compounds of the formula I.I" . The hydrogenation can be carried out analogously to known processes for reducing C=C double bonds [cf.: J. March, Advanced Organic Chemistry, 3rd ed. John Wiley & Sons 1985, pp. 690-700].
Figure imgf000011_0001
Advantageously, 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. Suitable are both heterogeneous catalysts, such as supported Pd or Pt catalysts, for example Pd on activated carbon, furthermore Pt02, and also homogeneous catalysts. The use of 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-Rc (formula I. II) can be prepared, for example, from compounds of the formula IVb.
Figure imgf000011_0002
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).
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.
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.
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].
Figure imgf000012_0001
Compounds of the formula I in which W is C-Rc and U is N (formula 1.111) can be obtained, for example, by reacting halopyridines of the formula IVc with hydrazides of the formula V.
Figure imgf000012_0002
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.
Compounds of the formula I in which W and U are N (formula I. IV) can be prepared, for example, f the formula IVc.
Figure imgf000012_0003
IVc I- IV
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 Γ obtainable by routes illustrated further above can be hydrogenated to given compounds of the formula I" . The hydrogenation can be carried out analogously to known processes for reducing C=C double bonds [cf.: J. March, Advanced Organic Chemistry, 3rd ed. John Wiley & Sons 1985, pp. 690-700; Peptide Chemistry 17, 1980, pp. 59-64; Tetrahedron Lett. 46, 1979, pp. 4483-4486]. In this manner, the compounds of the formula I.I" (W and U = C-Rc) are particularly easily obtainable from the corresponding unsaturated compounds Ι.Γ .
Figure imgf000013_0001
Advantageously, 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. Suitable are both heterogeneous catalysts, such as supported Pd or Pt catalysts, for example Pd on activated carbon, furthermore Pt02, and also homogeneous catalysts. The use of 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].
Various synthesis steps of the intermediates of the formulae II to IV in the routes illustrated above proceed in an advantageous manner if the group R1 is a protective group, such as, for example, pivaloyl or trimethylsilyl. If desired, this protective group can be cleaved off under generally known conditions at the stage of the formula I to release the compounds of the formula I in which R1 is hydrogen.
The 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.
If individual compounds I are not accessible via the above-described routes, they can be prepared by derivatization of other compounds I.
If the synthesis yields mixtures of isomers, a separation is generally however not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or during application (for example under the action of light, acids or bases). Such conversions may also take place after application, for example in the case of the treatment of plants in the treated plant or in the harmful plant to be controlled.
The organic moieties mentioned for the substituents of the compounds according to the invention are collective terms for individual enumerations of the individual group members. All hydrocarbon chains, such as alkyl, haloalkyl, alkenyl, alkynyl, and the alkyl moieties and alkenyl moieties in alkoxy, haloalkoxy, alkylamino, dialkylamino, N-alkylsulfonylamino, alkenyloxy, alkynyloxy, alkoxyamino, alkylaminosulfonylamino, dialkylaminosulfonylamino, alkenylamino, alkynylamino, N-(alkenyl)-N-(alkyl)amino, N-(alkynyl)-N-(alkyl)amino, N-(alkoxy)-N-(alkyl)amino, N-(alkenyl)-N-(alkoxy)amino or N-(alkynyl)-N-(alkoxy)amino can be straight-chain or branched.
The prefix Cn-Cm- indicates the respective number of carbons of the hydrocarbon unit. Unless indicated otherwise, halogenated substituents preferably carry one to five identical or different halogen atoms, in particular fluorine atoms or chlorine atoms.
The meaning halogen denotes in each case fluorine, chlorine, bromine or iodine.
Examples of other meanings are:
alkyl and the alkyl moieties for example in alkoxy, alkylamino, dialkylamino, N-alkyl- sulfonylamino, alkylaminosulfonylamino, dialkylaminosulfonylamino, N-(alkenyl)-N-
(alkyl)amino, N-(alkynyl)-N-(alkyl)amino, N-(alkoxy)-N-(alkyl)amino: saturated straight- chain or branched hydrocarbon radicals having one or more carbon atoms, for example 1 or 2, 1 to 4 or 1 to 6 carbon atoms, for example Ci-C6-alkyl, such as methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl, 1 ,1 -dimethylethyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, 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-dimethyl- butyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1 ,1 ,2-trimethyl- propyl, 1 ,2,2-trimethylpropyl, 1 -ethyl-1 -methylpropyl, 1 -ethyl-2-methylpropyl. In one embodiment according to the invention, alkyl denotes small alkyl groups, such as
Ci-C4-alkyl. In another embodiment according to the invention, 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-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1 -(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl,
1 - (bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl and nonafluorobutyl.
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,
2- butenyl, 3-butenyl, 1 -methyl-1 -propenyl, 2-methyl-1 -propenyl, 1 -methyl-2-propenyl, 2-methyl-2-propenyl, 1 -pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1 -methyl-1 - butenyl, 2-methyl-1 -butenyl, 3-methyl-1 -butenyl, 1-methyl-2-butenyl, 2-methyl-2- butenyl, 3-methyl-2-butenyl, 1 -methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3- butenyl, 1 ,1 -dimethyl-2-propenyl, 1 ,2-dimethyl-1 -propenyl, 1 ,2-dimethyl-2-propenyl,
1 - ethyl-1 -propenyl, 1 -ethyl-2-propenyl, 1 -hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1 -methyl-1 -pentenyl, 2-methyl-1 -pentenyl, 3-methyl-1 -pentenyl, 4-methyl-1 - pentenyl, 1 -methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2- pentenyl, 1 -methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3- pentenyl, 1 -methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4- pentenyl, 1 ,1 -dimethyl-2-butenyl, 1 ,1 -dimethyl-3-butenyl, 1 ,2-dimethyl-1 -butenyl, 1 ,2- dimethyl-2-butenyl, 1 ,2-dimethyl-3-butenyl, 1 ,3-dimethyl-1 -butenyl, 1 ,3-dimethyl-2- butenyl, 1 ,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2, 3-dimethyl-1 -butenyl, 2,3- dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3, 3-dimethyl-1 -butenyl, 3,3-dimethyl-2- butenyl, 1 -ethyl-1 -butenyl, 1 -ethyl-2-butenyl, 1 -ethyl-3-butenyl, 2-ethyl-1 -butenyl,
2- ethyl-2-butenyl, 2-ethyl-3-butenyl, 1 ,1 ,2-trimethyl-2-propenyl, 1 -ethyl-1 -methyl-2- propenyl, 1 -ethyl-2-methyl-1 -propenyl, 1 -ethyl-2-methyl-2-propenyl.
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,
1 - propynyl, 2-propynyl, 1 -butynyl, 2-butynyl, 3-butynyl, 1 -methyl-2-propynyl, 1 -pentynyl,
2- pentynyl, 3-pentynyl, 4-pentynyl, 1 -methyl-2-butynyl, 1 -methyl-3-butynyl, 2-methyl-3- butynyl, 3-methyl-1 -butynyl, 1 ,1 -dimethyl-2-propynyl, 1 -ethyl-2-propynyl, 1 -hexynyl,
2- hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1 -methyl-2-pentynyl, 1 -methyl-3-pentynyl,
1 - methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1 -pentynyl,
3- methyl-4-pentynyl, 4-methyl-1 -pentynyl, 4-methyl-2-pentynyl, 1 ,1 -dimethyl-2-butynyl, 1 ,1 -dimethyl-3-butynyl, 1 ,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1 - butynyl, 1 -ethyl-2-butynyl, 1 -ethyl-3-butynyl, 2-ethyl-3-butynyl, 1 -ethyl-1 -methyl-2- propynyl.
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,
1 ,1 ,2-trimethylpropoxy, 1 ,2,2-trimethylpropoxy, 1 -ethyl-1 -methylpropoxy or 1 -ethyl-2- methylpropoxy.
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,
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 thiazol-5-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. Another suitable ammonium cation is the pyridine nitrogen atom of the formula I quaternized by alkylation or arylation. Also suitable are phosphonium ions, sulfonium 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.
With respect to the variables, the particularly preferred embodiments of the intermediates correspond to those of the groups of the formula I .
In a particular embodiment, the 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 :
In a preferred embodiment of the compounds of the formula I , W and U are C-Rc, where Rc is preferably hydroge
Figure imgf000017_0001
In a further embodiment of the compounds of the formula I , W is N and U is C-Rc where Rc is preferably hydroge
Figure imgf000017_0002
In a preferred embodiment of the compounds of the formula I , U is N and W is C-Rc where Rc is preferably hydrogen.
Figure imgf000018_0001
In a preferred embodiment of the compounds of the formula I, W and U are N.
Figure imgf000018_0002
In a preferred embodiment of the compounds of the formula I, the two groups R3 and R4 together are a double bond.
These compounds correspond to the formula Γ :
Figure imgf000018_0003
In a further preferred embodiment of the compounds of the formula I, the groups R3 and R4 are groups Rc, in particular hydrogen.
These compounds correspond to the formula I" :
Figure imgf000018_0004
In a particularly preferred embodiment of the compounds of the formula I, A is N and E, G, M, W and U are C-Rc, and R3 and R4 are together a double bond. These compounds correspond to the formula 1.1
Figure imgf000018_0005
in which the groups Rc1, Rc2, Rc3, Rc4 and Rc5 each correspond to a group Rc and preferably have the following meanings:
Rc1 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H; Rc2 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyi, in particular H;
Rc3 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyi, in particular H;
Rc4 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyi, in particular H, Br, OH and OCH3;
Rc5 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyi, in particular H.
In a further embodiment of the compounds of the formula I, A and M are N and E, G, W and U are C-Rc, and the two groups R together are a double bond. These compounds correspond to the formula 1.2
Figure imgf000019_0001
in which the groups Rc1, Rc2, Rc3 and Rc4 each correspond to a group Rc and preferably have the following meanings:
Rc1 is H, OH, CN, halogen, alkyl, alkoxy, haolalkyl, in particular H;
Rc2 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyi, in particular H;
Rc3 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyi, in particular H;
Rc4 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyi, in particular H, Br, OH and OCH3.
In a further embodiment of the compounds of the formula I, A and M are N and E, G, W and U are C-Rc, and R3 and R4 together are a double bond. These compounds correspond to the formula 1.3
Figure imgf000019_0002
in which the groups Rc1, Rc2, Rc3 and Rc4 each correspond to a group Rc and preferably have the following meanings:
Rc1 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyi, in particular H;
Rc2 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyi, in particular H;
Rc3 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyi, in particular H, Br, OH and OCH3; Rc4 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyi, in particular H, Br, OH and OCH3.
In a further embodiment of the compounds of the formula I, A and E are N and B, M, W and U are C-Rc, and R3 and R4 together are a double bond. These compounds correspond to the formula 1.4
Figure imgf000020_0001
in which the groups Rc1, Rc2, Rc3 and Rc4 each correspond to a group Rc and preferably have the following meanings:
Rc1 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
Rc2 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
Rc3 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
Rc4 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H, Br, OH and OCH3.
In a further embodiment of the compounds of the formula I, A, E and G are C-Rc and M, W and U are N, and R3 and R4 together are a double bond. These compounds correspond to the formula
Figure imgf000020_0002
in which the groups Rc1, Rc2, Rc3, Rc4 and Rc5 each correspond to a group Rc and preferably have the following meanings:
Rc1 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
Rc2 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
Rc3 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H, Br, OH and OCH3; Rc4 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
Rc5 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H.
In a further embodiment of the compounds of the formula I, A is N and E, G, M, W and U are C-Rc, and R3 and R4 are hydrogen. These compounds correspond to the formula 1.6
I.6
Figure imgf000020_0003
in which the groups Rc1, Rc2, Rc3, Rc4 and Rc5 each correspond to a group Rc and preferably have the following meanings:
Rc1 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
Rc2 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
Rc3 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
Rc4 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H, Br, OH and OCH3; Rc5 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H.
In a further embodiment of the compounds of the formula I, A and U are N and E, G, M and W are C-Rc, and R3 and R4 together are a double bond. These compounds correspond to the formula
Figure imgf000021_0001
in which the groups Rc1, Rc2, Rc3 and Rc4 each correspond to a group Rc and preferably have the following meanings:
Rc1 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
Rc2 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
Rc3 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H, Br, OH and OCH3; Rc4 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H.
In a further embodiment of the compounds of the formula I, A, W and U are N and E, G and M are C-Rc, and R3 and R4 together are a double bond. These compounds correspond to the formula
Figure imgf000021_0002
in which the groups Rc1, Rc2 and Rc3 each correspond to a group Rc and preferably have the following meanings:
Rc1 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
Rc2 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H, Br, OH and OCH3;
Rc3 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H.
In a further embodiment of the compounds of the formula I, A and W are N and E, G, M and U are C-Rc, and R3 and R4 together are a double bond. These compounds correspond to the formula 1.9
Figure imgf000022_0001
in which the groups Rc1, Rc2, Rc3 and Rc4 each correspond to a group Rc and preferably have the following meanings:
Rc1 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
Rc2 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H;
Rc3 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H, Br, OH and OCH3; Rc4 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.
In a first preferred embodiment of the invention, R1 is 0-RA.
In a further preferred embodiment of the invention, R1 is S(0)n-RA where n is preferably 0 or 2, in particular 2.
In a further preferred embodiment, R1 is 0-S(0)n-RA, where n is preferably 0 or 2, in particular 2, such as, for example, OS(0)2-CH3, OS(0)2-C2H5, OS(0)2-C3H7, OS(0)2- C6H5 or OS(0)2-(4-CH3-C6H4).
In a further preferred embodiment, R1 is 0-S(0)n-NR'Rii, which has in particular the groups NR'R" mentioned below as being preferred.
RA is in particular H, Ci-C6-alkylcarbonyl, such as C(0)CH3, C(0)CH2CH3,
C(0)CH(CH3)2 or C(0)C(CH3)3; Ci-C6-cycloalkylcarbonyl, such as cyclopropylcarbonyl, cyclopentylcarbonyl or cyclohexylcarbonyl; C2-C6-alkenylcarbonyl, such as
C(0)CH=CH2 or C(0)CH2CH=CH2, optionally subst. benzoyl, such as C(0)C6H5, C(0)[2-CH3-C6H4], C(0)[4-CH3-C6H4], C(0)[2-F-C6H4], C(0)[4-F-C6H4], or optionally subst. heteroaryl, such as pyridine, which is attached via a carbonyl group. Particularly preferably, RA is H or Ci-C6-alkylcarbonyl.
More particularly preferably, RA is selected from the group consisting of H, OCH3, C(0)CH3, C(0)CH2CH3, C(0)CH(CH3)2, C(0)C(CH3)3, C(0)-c-C3H5, C(0)-C6H5, C(O)- CH2C6H5, C(0)CH2CI, C(0)CF3, C(0)CH2OCH3, C(0)N(CH3)2 and C(0)OCH2CH3.
In a further preferred embodiment of the invention, RA is NR'R".
In a further preferred embodiment of the invention, RA is Z-NR'-C(0)-NR'R'', where R' and R" are as defined at the outset and preferably as defined below. In further embodiments, Ci-C4-alkoxy, Ci-C4-haloalkoxy and Ci-C4-alkoxy-Ci-C4-alkyl, in particular OCH3, OC2H5, CH2CH2OCH3 and CH2CH2CI, may also be possible for R' and R", independently of one another.
R< and R" are preferably d-Cs-alkyl, Ci-C4-haloalkyl, Z-C3-C6-cycloalkyl, Z-Ci-C8- alkoxy, Z-Ci-Cs-haloalkoxy, Z-phenyl, Z-C(=0)-Ra or Z-hetaryl. Here, preference is given to CH3, C2H5, n-propyl, CH(CH3)2, butyl, 2-chloroethyl, cyclopentyl, cyclohexyl, 2-ethoxymethyl, 2-chloroethoxy, phenyl, pyrimidines or triazines whose rings are unsubstituted or substituted. Here, preferred substituents are Ci-C4-alkylcarbonyl or Ci-C4-haloalkylcarbonyl, in particular C(=0)-CH3, C(=0)-C2H5, C(=0)-C3H7, C(=0)- CH(CH3)2, butylcarbonyl and C(=0)-CH2CI. Particularly preferred aspects of the group NR'R" are N(di-Ci-C4-alkyl), in particular N(CH3)-Ci-C4-alkyl, such as N(CH3)2,
N(CH3)CH2CH3, N(CH3)C3H7 and N(CH3)CH(CH3)2.
Further particularly preferred aspects of 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, CH3, halo-Ci-C2-alkyl, halo-Ci-C2-alkoxy and carboxyl groups, such as 2-CI-6-COOH-C6H3, 2,6-CI2-C6H3, 2,6-F2-C6H3, 2,6-CI2-3-CH3-C6H2, 2- CF3-6-CH2CHF2-C6H3, 2-CF3-6-OCF3-C6H3 and 2-CF3-6-CH2CHF2-C6H3.
Further aspects of 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-C4-alkoxy and/or halogen. Particular preference is given to 5,7-dimethoxy-[1 ,2,4]triazolo[1 ,5-a]pyrimidin-2-yl, 5,7-diethoxy-[1 ,2,4]- triazolo[1 ,5-a]pyrimidin-2-yl, 5-fluoro-7-methoxy-[1 ,2,4]triazolo[1 ,5-a]pyrimidin-2-yl and 5-fluoro-7-ethoxy-[1 ,2,4]triazolo[1 ,5-a]pyrimidin-2-yl.
In particularly preferred embodiments of the compounds of the formula I and in particular those of the formula 1.1 , R1 is selected from the group consisting of OH, OCH3, OC(0)CH3, OC(0)CH2CH3, OC(0)CH(CH3)2, OC(0)C(CH3)3, OC(0)-c-C3H5, OC(0)-C6H5, OC(0)-CH2C6H5, OC(0)CH2CI, OC(0)-CF3, OC(0)-CH2OCH3, OC(O)- N(CH3)2 and OC(0)-OCH2CH3.
In particularly preferred embodiments of the compounds of the formula I and in particular those of the formula 1.1 , R2 is phenyl which is substituted by a group selected from the group consisting of 2-Br, 2-CI, 2,4-CI2, 2-CI-4-F, 2-CI-5-F, 2-CI-6-F, 2-CI-4- CF3, 2-CI-5-CF3, 2-CI-6-CF3, 2-CI-3,6-F2, 2-F, 2,4-F2, 2,5-F2, 2,6-F2, 2-F-4-CF3, 2-F-5- CF3, 2-F-6-CF3, 2,3,6-F3, 2-N02, 2-N02-4-F, 2-N02-5-F, 2-N02-6-F, 2-N02-4-CF3, 2- N02-5-CF3, 2-N02-6-CF3, 2-N02-3,6-F2, 2-CN, 2-CH3, 2-CH3-4-F, 2-CH3-5-F, 2-CH3-6- F, 2-CH3-4-CF3, 2-CH3-5-CF3, 2-CH3-6-CF3, 2-CH3-3,6-F2, 2-OCH3, 2-OCH3-4-F, 2- OCH3-5-F, 2-OCH3-6-F, 2-OCH3-4-CF3, 2-OCH3-5-CF3, 2-OCH3-6-CF3, 2-OCH3-3,6-F2, 2-CHF2, 2-CHF2-4-F, 2-CHF2-5-F, 2-CHF2-6-F, 2-CHF2-4-CF3, 2-CHF2-5-CF3, 2-CHF2- 6-CF3, 2-CHF2-3,6-F2, 2-CF3, 2-CF3-4-F, 2-CF3-5-F, 2-CF3-6-F, 2-CF3-4-CF3, 2-CF3-5- CF3, 2-CF3-6-CF3, 2-CF3-3,6-F2, 2-OCHF2, 2-OCHF2-4-F, 2-OCHF2-5-F, 2-OCHF2-6-F, 2-OCHF2-4-CF3, 2-OCHF2-5-CF3, 2-OCHF2-6-CF3, 2-OCHF2-3,6-F2, 2-OCF3, 2-OCF3- 4-F, 2-OCF3-5-F, 2-OCF3-6-F, 2-OCF3-4-CF3, 2-OCF3-5-CF3, 2-OCF3-6-CF3 and 2- OCF3-3,6-F2.
In a further preferred embodiment of the invention, RA is a 5- or 6-membered heterocycle optionally substituted by Rb 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 Rb. Preference is given to saturated or unsaturated groups attached via nitrogen, such as, for example:
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 thiazol-5-yl;
In another aspect, RA 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 Rb.
Preferred groups Rb are in particular F, CI, CN, N02, CH3, C2H5, OCH3, OC2H5,
Figure imgf000024_0001
In a further preferred aspect, R2 is phenyl which is unsubstituted or partially or fully substituted by groups Rb. Particular preference is given to compounds in which a group Rb is located in the ortho-position. Such compounds of the formula I are described by the formula I. A:
Figure imgf000024_0002
In formula I.A, the index m is zero or an integer from one to four, preferably 0, 1 or 2, in particular 0 or 1. R5 and R6 are groups Rb as defined at the outset, preferably halogen, NO2, Ci-C4-alkyl, Ci-C2-haloalkyl and Ci-C4-alkoxy. One group R6 is preferably located in position 5. A group R6 in position 3 is a further preferred embodiment.
Particularly preferably, R5 is Br, F, N02, CN, CH3, OCH3, CF3, OCF3, CHF2 or OCHF2. R6 is particularly preferably halogen or halomethyl, such as CI, F or CF3.
Especially preferably, (R6)m is selected from the group consisting of 4-F, 5-F, 5-CI, 6-F, 4-CFs, 5-CFs and 3,6-F2.
R3 is preferably H, Ci-C6-alkyl, such as CH3, C2H5, n-C3H7, CH(CH3)2, n-C3H9, or C(CH3)3; C3-C6-cycloalkyl-Ci-C4-alkyl, such as cyclopropylmethyl, C3-C6-alkenyl, such as CH2CH=CH2, CH2C(CH3)=CH2, CH2CH2H=CH2, CH2CH2C(CH3)-CH2, CH2CH2CH2CH=CH2, CH2CH2CH2C(CH3)=CH2, or optionally subst. phenyl, such as C6H5, 4-CH3-C6H4, 4-F-C6H4 or S(0)n-RN, where RN is Ci-C6-haloalkyl, such as CH2CF3,
Rc is preferably Η,ΟΗ, 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.
In particular with a view to their use, preference is given to the compounds of the formula I compiled in the tables below, which compounds correspond to the formulae 1.1 A*, I.2A*, I.3A*, I.4A* and I.5A*. The groups mentioned for a substituent in the tables are furthermore per se, independently of the combination in which they are mentioned, a particularly preferred aspect of the substituent in question.
Figure imgf000025_0001
Table 1
Compounds of the formula 1.1 A*, in which the index m in (R6)m is zero and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 2
Compounds of the formula 1.1 A*, in which (R6)m is 4-CI and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 3
Compounds of the formula 1.1 A*, in which (R6)m is 3-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 4
Compounds of the formula 1.1 A*, in which (R6)m is 4-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 5
Compounds of the formula 1.1 A*, in which (R6)m is 5-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 6
Compounds of the formula 1.1 A*, in which (R6)m is 6-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 7
Compounds of the formula 1.1 A*, in which (R6)m is 4-CF3 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 8
Compounds of the formula 1.1 A*, in which (R6)m is 5-CF3 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 9
Compounds of the formula 1.1 A*, in which (R6)m is 3,6-F2 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 10
Compounds of the formula I.2A*, in which the index m in (R6)m is zero and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 1 1
Compounds of the formula I.2A*, in which (R6)m is 4-CI and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 12
Compounds of the formula I.2A*, in which (R6)m is 3-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 13
Compounds of the formula I.2A*, in which (R6)m is 4-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A Table 14
Compounds of the formula I.2A*, in which (R6)m is 5-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 15
Compounds of the formula I.2A*, in which (R6)m is 6-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 16
Compounds of the formula I.2A*, in which (R6)m is 4-CF3 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 17
Compounds of the formula I.2A*, in which (R6)m is 5-CF3 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 18
Compounds of the formula I.2A*, in which (R6)m is 3,6-F2 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 19
Compounds of the formula I.3A*, in which the index m in (R6)m is zero and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 20
Compounds of the formula I.3A*, in which (R6)m is 4-CI and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 21
Compounds of the formula I.3A*, in which (R6)m is 3-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 22
Compounds of the formula I.3A*, in which (R6)m is 4-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 23
Compounds of the formula I.3A*, in which (R6)m is 5-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 24
Compounds of the formula I.3A*, in which (R6)m is 6-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 25
Compounds of the formula I.3A*, in which (R6)m is 4-CF3 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 26
Compounds of the formula I.3A*, in which (R6)m is 5-CF3 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A Table 27
Compounds of the formula I.3A*, in which (R6)m is 3,6-F2 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 28
Compounds of the formula I.4A*, in which the index m in (R6)m is zero and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 29
Compounds of the formula I.4A*, in which (R6)m is 4-CI and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 30
Compounds of the formula I.4A*, in which (R6)m is 3-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 31
Compounds of the formula 1.4A*, in which (R6)m is 4-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 32
Compounds of the formula I.4A*, in which (R6)m is 5-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 33
Compounds of the formula I.4A*, in which (R6)m is 6-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 34
Compounds of the formula I.4A*, in which (R6)m is 4-CF3 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 35
Compounds of the formula I.4A*, in which (R6)m is 5-CF3 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 36
Compounds of the formula I.4A*, in which X is oxygen, (R6)m is 3,6-F2 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 37
Compounds of the formula I.5A*, in which the index m in (R6)m is zero and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 38
Compounds of the formula I.5A*, in which (R6)m is 4-CI and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 39
Compounds of the formula I.5A*, in which (R6)m is 3-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A Table 40
Compounds of the formula I.5A*, in which (R6)m is 4-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 41
Compounds of the formula I.5A*, in which (R6)m is 5-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 42
Compounds of the formula I.5A*, in which (R6)m is 6-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 43
Compounds of the formula I.5A*, in which (R6)m is 4-CF3 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 44
Compounds of the formula I.5A*, in which (R6)m is 5-CF3 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 45
Compounds of the formula I.5A*, in which (R6)m is 3,6-F2 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 46
Compounds of the formula I.6A*, in which (R6)m is 4-CI and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 47
Compounds of the formula I.6A*, in which (R6)m is 3-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 48
Compounds of the formula I.6A*, in which (R6)m is 4-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 49
Compounds of the formula I.6A*, in which (R6)m is 5-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 50
Compounds of the formula I.6A*, in which X is sulfur, (R6)m is 6-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 51
Compounds of the formula I.6A*, in which (R6)m is 4-CF3 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 52
Compounds of the formula I.6A*, in which (R6)m is 5-CF3 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 53
Compounds of the formula I.6A*, in which (R6)m is 3,6-F2 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A Table 54
Compounds of the formula I.7A*, in which (R6)m is 4-CI and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 55
Compounds of the formula I.7A*, in which (R6)m is 3-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 56
Compounds of the formula I.7A*, in which (R6)m is 4-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 57
Compounds of the formula I.7A*, in which (R6)m is 5-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 58
Compounds of the formula I.7A*, in which (R6)m is 6-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 59
Compounds of the formula I.7A*, in which (R6)m is 4-CF3 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 60
Compounds of the formula I.7A*, in which (R6)m is 5-CF3 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 61
Compounds of the formula I.7A*, in which (R6)m is 3,6-F2 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 62
Compounds of the formula I.8A*, in which (R6)m is 4-CI and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 63
Compounds of the formula I.8A*, in which (R6)m is 3-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 64
Compounds of the formula I.8A*, in which (R6)m is 4-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 65
Compounds of the formula I.8A*, in which (R6)m is 5-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 66
Compounds of the formula I.8A*, in which (R6)m is 6-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 67
Compounds of the formula I.8A*, in which (R6)m is 4-CF3 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A Table 68
Compounds of the formula I.8A*, in which (R6)m is 5-CF3 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 69
Compounds of the formula I.8A*, in which (R6)m is 3,6-F2 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 70
Compounds of the formula I.9A*, in which the index m in (R6)m is zero and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 71
Compounds of the formula I.9A*, in which (R6)m is 4-CI and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 72
Compounds of the formula 1.9A*, in which (R6)m is 3-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 73
Compounds of the formula I.9A*, in which (R6)m is 4-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 74
Compounds of the formula I.9A*, in which (R6)m is 5-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 75
Compounds of the formula I.9A*, in which (R6)m is 6-F and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 76
Compounds of the formula I.9A*, in which (R6)m is 4-CF3 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 77
Compounds of the formula I.9A*, in which (R6)m is 5-CF3 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table 78
Compounds of the formula I.9A*, in which (R6)m is 3,6-F2 and the combination of R1 and R5 for a compound corresponds in each case to one row of Table A
Table A
No. R R5 No. R R5
A-1 OH Br A-7 OC(0)-c-C3H5 Br
A-2 OCH3 Br A-8 OC(0)-C6H5 Br
A-3 OC(0)CH3 Br A-9 OC(0)-CH2C6H5 Br
A-4 OC(0)CH2CH3 Br A-10 OC(0)CH2CI Br
A-5 OC(0)CH(CH3)2 Br A-1 1 OC(0)-CF3 Br
A-6 OC(0)C(CH3)3 Br A-12 OC(0)-CH2OCH3 Br No. R R5 No. R R5
A-13 OC(0)-N(CH3)2 Br A-52 OS(0)2-T2 CI
A-14 OC(0)-OCH2CH3 Br A-53 OS(0)2-T3 CI
A-15 OS(0)2-CH3 Br A-54 OS(0)2-T4 CI
A-16 OS(0)2-C2H5 Br A-55 OS(0)2-T5 CI
A-17 OS(0)2-C3H7 Br A-56 OS(0)2-T6 CI
A-18 OS(0)2-CH(CH3)2 Br A-57 OS(0)2-T7 CI
A-19 OS(0)2-C6H5 Br A-58 OS(0)2-T8 CI
A-20 OS(0)2-T1 Br A-59 OS(0)2-T9 CI
A-21 OS(0)2-T2 Br A-60 OS(O)2-T10 CI
A-22 OS(0)2-T3 Br A-61 0S(0)2-T1 1 CI
A-23 OS(0)2-T4 Br A-62 OS(0)2-T12 CI
A-24 OS(0)2-T5 Br A-63 OH F
A-25 OS(0)2-T6 Br A-64 OCH3 F
A-26 OS(0)2-T7 Br A-65 OC(0)CH3 F
A-27 OS(0)2-T8 Br A-66 OC(0)CH2CH3 F
A-28 OS(0)2-T9 Br A-67 OC(0)CH(CH3)2 F
A-29 OS(O)2-T10 Br A-68 OC(0)C(CH3)3 F
A-30 OS(0)2-T1 1 Br A-69 OC(0)-c-C3H5 F
A-31 OS(0)2-T12 Br A-70 OC(0)-C6H5 F
A-32 OH CI A-71 OC(0)-CH2C6H5 F
A-33 OCH3 CI A-72 OC(0)CH2CI F
A-34 OC(0)CH3 CI A-73 OC(0)-CF3 F
A-35 OC(0)CH2CH3 CI A-74 OC(0)-CH2OCH3 F
A-36 OC(0)CH(CH3)2 CI A-75 OC(0)-N(CH3)2 F
A-37 OC(0)C(CH3)3 CI A-76 OC(0)-OCH2CH3 F
A-38 OC(0)-c-C3H5 CI A-77 OS(0)2-CH3 F
A-39 OC(0)-C6H5 CI A-78 OS(0)2-C2H5 F
A-40 OC(0)-CH2C6H5 CI A-79 OS(0)2-C3H7 F
A-41 OC(0)CH2CI CI A-80 OS(0)2-CH(CH3)2 F
A-42 OC(0)-CF3 CI A-81 OS(0)2-C6H5 F
A-43 OC(0)-CH2OCH3 CI A-82 OS(0)2-T1 F
A-44 OC(0)-N(CH3)2 CI A-83 OS(0)2-T2 F
A-45 OC(0)-OCH2CH3 CI A-84 OS(0)2-T3 F
A-46 OS(0)2-CH3 CI A-85 OS(0)2-T4 F
A-47 OS(0)2-C2H5 CI A-86 OS(0)2-T5 F
A-48 OS(0)2-C3H7 CI A-87 OS(0)2-T6 F
A-49 OS(0)2-CH(CH3)2 CI A-88 OS(0)2-T7 F
A-50 OS(0)2-C6H5 CI A-89 OS(0)2-T8 F
A-51 OS(0)2-T1 CI A-90 OS(0)2-T9 F No. R R5 No. R R5
A-91 OS(O)2-T10 F A-130 OC(0)C(CH3)3 CN
A-92 OS(0)2-T1 1 F A-131 OC(0)-c-C3H5 CN
A-93 OS(0)2-T12 F A-132 OC(0)-C6H5 CN
A-94 OH N02 A-133 OC(0)-CH2C6H5 CN
A-95 OCHs N02 A-134 OC(0)CH2CI CN
A-96 OC(0)CH3 N02 A-135 OC(0)-CF3 CN
A-97 OC(0)CH2CH3 N02 A-136 OC(0)-CH2OCH3 CN
A-98 OC(0)CH(CH3)2 N02 A-137 OC(0)-N(CH3)2 CN
A-99 OC(0)C(CH3)3 N02 A-138 OC(0)-OCH2CH3 CN
A-100 OC(0)-c-C3H5 N02 A-139 OS(0)2-CH3 CN
A-101 OC(0)-C6H5 N02 A-140 OS(0)2-C2H5 CN
A-102 OC(0)-CH2C6H5 N02 A-141 OS(0)2-C3H7 CN
A-103 OC(0)CH2CI N02 A-142 OS(0)2-CH(CH3)2 CN
A-104 OC(0)-CF3 N02 A-143 OS(0)2-C6H5 CN
A-105 OC(0)-CH2OCH3 N02 A-144 OS(0)2-T1 CN
A-106 OC(0)-N(CH3)2 N02 A-145 OS(0)2-T2 CN
A-107 OC(0)-OCH2CH3 N02 A-146 OS(0)2-T3 CN
A-108 OS(0)2-CH3 N02 A-147 OS(0)2-T4 CN
A-109 OS(0)2-C2H5 N02 A-148 OS(0)2-T5 CN
A-110 OS(0)2-C3H7 N02 A-149 OS(0)2-T6 CN
A-11 1 OS(0)2-CH(CH3)2 N02 A-150 OS(0)2-T7 CN
A-112 OS(0)2-C6H5 N02 A-151 OS(0)2-T8 CN
A-113 OS(0)2-T1 N02 A-152 OS(0)2-T9 CN
A-114 OS(0)2-T2 N02 A-153 OS(O)2-T10 CN
A-115 OS(0)2-T3 N02 A-154 OS(0)2-T1 1 CN
A-116 OS(0)2-T4 N02 A-155 OS(0)2-T12 CN
A-117 OS(0)2-T5 N02 A-156 OH CH3
A-118 OS(0)2-T6 N02 A-157 OCH3 CH3
A-119 OS(0)2-T7 N02 A-158 OC(0)CH3 CH3
A-120 OS(0)2-T8 N02 A-159 OC(0)CH2CH3 CH3
A-121 OS(0)2-T9 N02 A-160 OC(0)CH(CH3)2 CH3
A-122 OS(O)2-T10 N02 A-161 OC(0)C(CH3)3 CH3
A-123 OS(0)2-T1 1 N02 A-162 OC(0)-c-C3H5 CH3
A-124 OS(0)2-T12 N02 A-163 OC(0)-C6H5 CH3
A-125 OH CN A-164 OC(0)-CH2C6H5 CH3
A-126 OCH3 CN A-165 OC(0)CH2CI CH3
A-127 OC(0)CH3 CN A-166 OC(0)-CF3 CH3
A-128 OC(0)CH2CH3 CN A-167 OC(0)-CH2OCH3 CH3
A-129 OC(0)CH(CH3)2 CN A-168 OC(0)-N(CH3)2 CH3 No. R R5 No. R R5
A-169 OC(0)-OCH2CH3 CH3 A-208 OS(0)2-T3 OCH3
A-170 OS(0)2-CH3 CH3 A-209 OS(0)2-T4 OCH3
A-171 OS(0)2-C2H5 CH3 A-210 OS(0)2-T5 OCH3
A-172 OS(0)2-C3H7 CH3 A-21 1 OS(0)2-T6 OCH3
A-173 OS(0)2-CH(CH3)2 CH3 A-212 OS(0)2-T7 OCH3
A-174 OS(0)2-C6H5 CH3 A-213 OS(0)2-T8 OCH3
A-175 OS(0)2-T1 CH3 A-214 OS(0)2-T9 OCH3
A-176 OS(0)2-T2 CH3 A-215 OS(O)2-T10 OCH3
A-177 OS(0)2-T3 CH3 A-216 OS(0)2-T1 1 OCH3
A-178 OS(0)2-T4 CH3 A-217 OS(0)2-T12 OCH3
A-179 OS(0)2-T5 CH3 A-218 OH CHF2
A-180 OS(0)2-T6 CH3 A-219 OCH3 CHF2
A-181 OS(0)2-T7 CH3 A-220 OC(0)CH3 CHF2
A-182 OS(0)2-T8 CH3 A-221 OC(0)CH2CH3 CHF2
A-183 OS(0)2-T9 CH3 A-222 OC(0)CH(CH3)2 CHF2
A-184 OS(O)2-T10 CH3 A-223 OC(0)C(CH3)3 CHF2
A-185 OS(0)2-T1 1 CH3 A-224 OC(0)-c-C3H5 CHF2
A-186 OS(0)2-T12 CH3 A-225 OC(0)-C6H5 CHF2
A-187 OH OCH3 A-226 OC(0)-CH2C6H5 CHF2
A-188 OCH3 OCH3 A-227 OC(0)CH2CI CHF2
A-189 OC(0)CH3 OCH3 A-228 OC(0)-CF3 CHF2
A-190 OC(0)CH2CH3 OCH3 A-229 OC(0)-CH2OCH3 CHF2
A-191 OC(0)CH(CH3)2 OCH3 A-230 OC(0)-N(CH3)2 CHF2
A-192 OC(0)C(CH3)3 OCH3 A-231 OC(0)-OCH2CH3 CHF2
A-193 OC(0)-c-C3H5 OCH3 A-232 OS(0)2-CH3 CHF2
A-194 OC(0)-C6H5 OCH3 A-233 OS(0)2-C2H5 CHF2
A-195 OC(0)-CH2C6H5 OCH3 A-234 OS(0)2-C3H7 CHF2
A-196 OC(0)CH2CI OCH3 A-235 OS(0)2-CH(CH3)2 CHF2
A-197 OC(0)-CF3 OCH3 A-236 OS(0)2-C6H5 CHF2
A-198 OC(0)-CH2OCH3 OCH3 A-237 OS(0)2-T1 CHF2
A-199 OC(0)-N(CH3)2 OCH3 A-238 OS(0)2-T2 CHF2
A-200 OC(0)-OCH2CH3 OCH3 A-239 OS(0)2-T3 CHF2
A-201 OS(0)2-CH3 OCH3 A-240 OS(0)2-T4 CHF2
A-202 OS(0)2-C2H5 OCH3 A-241 OS(0)2-T5 CHF2
A-203 OS(0)2-C3H7 OCH3 A-242 OS(0)2-T6 CHF2
A-204 OS(0)2-CH(CH3)2 OCH3 A-243 OS(0)2-T7 CHF2
A-205 OS(0)2-C6H5 OCH3 A-244 OS(0)2-T8 CHF2
A-206 OS(0)2-T1 OCH3 A-245 OS(0)2-T9 CHF2
A-207 OS(0)2-T2 OCH3 A-246 OS(O)2-T10 CHF2 No. R R5 No. R R5
A-247 OS(0)2-T1 1 CHF2 A-286 OC(0)-c-C3H5 OCHF2
A-248 OS(0)2-T12 CHF2 A-287 OC(0)-C6H5 OCHF2
A-249 OH CF3 A-288 OC(0)-CH2C6H5 OCHF2
A-250 OCHs CF3 A-289 OC(0)CH2CI OCHF2
A-251 OC(0)CH3 CF3 A-290 OC(0)-CF3 OCHF2
A-252 OC(0)CH2CH3 CF3 A-291 OC(0)-CH2OCH3 OCHF2
A-253 OC(0)CH(CH3)2 CF3 A-292 OC(0)-N(CH3)2 OCHF2
A-254 OC(0)C(CH3)3 CF3 A-293 OC(0)-OCH2CH3 OCHF2
A-255 OC(0)-c-C3H5 CF3 A-294 OS(0)2-CH3 OCHF2
A-256 OC(0)-C6H5 CF3 A-295 OS(0)2-C2H5 OCHF2
A-257 OC(0)-CH2C6H5 CF3 A-296 OS(0)2-C3H7 OCHF2
A-258 OC(0)CH2CI CF3 A-297 OS(0)2-CH(CH3)2 OCHF2
A-259 OC(0)-CF3 CF3 A-298 OS(0)2-C6H5 OCHF2
A-260 OC(0)-CH2OCH3 CF3 A-299 OS(0)2-T1 OCHF2
A-261 OC(0)-N(CH3)2 CF3 A-300 OS(0)2-T2 OCHF2
A-262 OC(0)-OCH2CH3 CF3 A-301 OS(0)2-T3 OCHF2
A-263 OS(0)2-CH3 CF3 A-302 OS(0)2-T4 OCHF2
A-264 OS(0)2-C2H5 CF3 A-303 OS(0)2-T5 OCHF2
A-265 OS(0)2-C3H7 CF3 A-304 OS(0)2-T6 OCHF2
A-266 OS(0)2-CH(CH3)2 CF3 A-305 OS(0)2-T7 OCHF2
A-267 OS(0)2-C6H5 CF3 A-306 OS(0)2-T8 OCHF2
A-268 OS(0)2-T1 CF3 A-307 OS(0)2-T9 OCHF2
A-269 OS(0)2-T2 CF3 A-308 OS(O)2-T10 OCHF2
A-270 OS(0)2-T3 CF3 A-309 OS(0)2-T1 1 OCHF2
A-271 OS(0)2-T4 CF3 A-310 OS(0)2-T12 OCHF2
A-272 OS(0)2-T5 CF3 A-31 1 OH OCF3
A-273 OS(0)2-T6 CF3 A-312 OCH3 OCF3
A-274 OS(0)2-T7 CF3 A-313 OC(0)CH3 OCF3
A-275 OS(0)2-T8 CF3 A-314 OC(0)CH2CH3 OCF3
A-276 OS(0)2-T9 CF3 A-315 OC(0)CH(CH3)2 OCF3
A-277 OS(O)2-T10 CF3 A-316 OC(0)C(CH3)3 OCF3
A-278 OS(0)2-T1 1 CF3 A-317 OC(0)-c-C3H5 OCF3
A-279 OS(0)2-T12 CF3 A-318 OC(0)-C6H5 OCF3
A-280 OH OCHF2 A-319 OC(0)-CH2C6H5 OCF3
A-281 OCH3 OCHF2 A-320 OC(0)CH2CI OCF3
A-282 OC(0)CH3 OCHF2 A-321 OC(0)-CF3 OCF3
A-283 OC(0)CH2CH3 OCHF2 A-322 OC(0)-CH2OCH3 OCF3
A-284 OC(0)CH(CH3)2 OCHF2 A-323 OC(0)-N(CH3)2 OCF3
A-285 OC(0)C(CH3)3 OCHF2 A-324 OC(0)-OCH2CH3 OCF3
Figure imgf000036_0001
T1 = NH(4-CH3-C6H4)
T2 = N(CH3)2
T3 = N(CH3)CH2CH3
T4 = N(CH3)C3H7
T5 = N(CH3)CH(CH3)2
T6 = NH(2-CI-6-COOH-C6H3)
T7 = NH(2,6-CI2-C6H3)
T8 = NH(2,6-F2-C6H3)
T9 = NH(2,6-CI2-3-CH3-C6H2)
T10 = : NH(2-CF3-6-CH2CHF2-C6H3)
T1 1 = : NH(2-CF3-6-OCF3-C6H3)
T12 = : NH(2-CF3-6-OCH2CHF2-C6H3) 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 herbicidal compositions comprising the compound I, in particular the preferred aspects thereof, control vegetation on non- crop areas very efficiently, especially at high rates of application. They act against broad-leaved weeds and weed grasses in crops such as wheat, rice, corn, soybeans and cotton without causing any significant damage to the crop plants. This effect is mainly observed at low rates of application.
Depending on the application method in question, 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. Examples of suitable crops are the following:
Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Avena sativa, Beta vulgaris spec, altissima, Beta vulgaris spec, rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Brassica oleracea, Brassica nigra, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec, Manihot esculenta, Medicago sativa, Musa spec, Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec, Pistacia vera, Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Prunus armeniaca, Prunus cerasus, Prunus dulcis and Prunus domestica, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Sinapis alba, Solanum tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticale, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.
The term "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). Here, in general, one or more genes are integrated into the genetic material of the plant to improve the properties of the plant.
Accordingly, the term "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,
WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073), enolpyruvylshikimate 3-phosphate synthase (EPSPS) inhibitors, such as, for example, glyphosate (see, for example, WO 92/00377), glutamine synthetase (GS) inhibitors, such as, for example, glufosinate (see, for example, EP-A-0242236, EP-A-242246), or oxynil herbicides (see, for example, US 5,559,024).
Numerous crop plants, for example Clearfield® oilseed rape, tolerant to
imidazolinones, for example imazamox, have been generated with the aid of classic breeding methods (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.
Accordingly, the term "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;
receptors of the diuretic hormone (helicokinin receptors); stilbene synthase, bibenzyl synthase, chitinases and glucanases. In the plants, 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. The methods for producing these genetically modified plants are known to the person skilled in the art and disclosed, for example, in the publications mentioned above. Numerous of the toxins mentioned above bestow, upon the plants by which they are produced, tolerance to pests from all taxonomic classes of arthropods, in particular to beetles (Coeleropta), dipterans (Diptera) and butterflies (Lepidoptera) and to
nematodes (Nematoda).
Genetically modified plants which produce one or more genes coding for insecticidal toxins are described, for example, in the publications mentioned above, and some of them are commercially available, such as, for example, YieldGard® (corn varieties producing the toxin Cry1 Ab), YieldGard® Plus (corn varieties which produce the toxins CrylAb and Cry3Bb1 ), Starlink® (corn varieties which produce the toxin Cry9c), Herculex® RW (corn varieties which produce the toxins Cry34Ab1 , Cry35Ab1 and the enzyme phosphinothricin-N-acetyltransferase [PAT]); NuCOTN® 33B (cotton varieties which produce the toxin CrylAc), Bollgard® I (cotton varieties which produce the toxin Cry1 Ac), Bollgard® II (cotton varieties which produce the toxins CrylAc and Cry2Ab2); VIPCOT® (cotton varieties which produce a VIP toxin); NewLeaf® (potato varieties which produce the toxin Cry3A); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt1 1 (for example Agrisure® CB) and Bt176 from Syngenta Seeds SAS,
France (corn varieties which produce the toxin CrylAb and the PAT enyzme), MIR604 from Syngenta Seeds SAS, France (corn varieties which produce a modified version of the toxin Cry3A, see WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium (corn varieties which produce the toxin Cry3Bb1 ), IPC 531 from Monsanto Europe S.A., Belgium (cotton varieties which produce a modified version of the toxin CrylAc) and 1507 from Pioneer Overseas Corporation, Belgium (corn varieties which produce the toxin Cry1 F and the PAT enzyme).
Accordingly, the term "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).
Accordingly, the term "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.
The term "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).
The term "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).
Furthermore, it has been found that 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. In this regard there have been found 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.
As desiccants, 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.
Moreover, a shortening of the time interval in which the individual cotton plants mature leads to an increased fiber quality after harvesting.
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.
Examples of 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. Examples of 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) are polysaccharides, such as xanthan gum (Kelzan® from Kelco), Rhodopol® 23 (Rhone Poulenc) or Veegum® (from R.T. Vanderbilt), and also organic and inorganic sheet minerals, such as Attaclay® (from Engelhardt).
Examples of antifoams are 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.
Examples of bactericides are 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).
Examples of antifreeze agents are ethylene glycol, propylene glycol, urea or glycerol. Examples of 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.
Examples of 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.
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.
Suitable surfactants (adjuvants, wetting agents, tackifiers, dispersants and also emulsifiers) are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, for example lignosulfonic acids (e.g. Borrespers-types, Borregaard), phenolsulfonic acids, naphthalenesulfonic acids (Morwet types, Akzo Nobel) and dibutylnaphthalenesulfonic acid (Nekal types, BASF SE), and of fatty acids, alkyi- and alkylarylsulfonates, alkyi sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and also of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl or tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyi ethers or polyoxypropylene alkyi ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite waste liquors and proteins, denatured proteins, polysaccharides (e.g. 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. To prepare 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. Alternatively, it is also possible to prepare concentrates comprising active substance, wetting agent, tackifier, dispersant or emulsifier and, if desired, solvent or oil, which are suitable for dilution with water.
The concentrations of the compounds of the formula I in the ready-to-use
preparations can be varied within wide ranges. In general, 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:
1 . Products for dilution with water A Water-soluble concentrates
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.
B Dispersible concentrates
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. The active compound content is 20% by weight.
C Emulsifiable concentrates
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.
D Emulsions
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). 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. The formulation has an active compound content of 25% by weight.
E Suspensions
In an agitated ball mill, 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.
F Water-dispersible granules and water-soluble granules
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.
G Water-dispersible powders and water-soluble powders
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.
H Gel formulations
In a ball mill, 20 parts by weight of active compound, 10 parts by weight of dispersant, 1 part by weight of gelling agent and 70 parts by weight of water or of an organic solvent are ground to give a fine suspension. Dilution with water gives a stable suspension with active compound content of 20% by weight.
2. Products to be applied undiluted
I Dusts
5 parts by weight of active compound are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dusting powder with an active compound content of 5% by weight.
J Granules (GR, FG, GG, MG)
0.5 parts by weight of active compound are ground finely and associated with
99.5 parts by weight of carriers. Current methods here are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted with an active compound content of 0.5% by weight.
K ULV solutions (UL)
10 parts by weight of active compound are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product to be applied undiluted with an active compound content of 10% 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).
In a further embodiment, 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. Here, the herbicidal compositions can be applied diluted or undiluted.
The term seed comprises seed of all types, such as, for example, corns, seeds, fruits, tubers, cuttings and similar forms. Here, preferably, the term 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. To treat the seed, the compounds I are generally employed in amounts of from 0.001 to 10 kg per 100 kg of seed.
It may also be advantageous to use the compounds of the formula I in combination with safeners. 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-alkylcarbamates and their agriculturally useful salts and, provided that they have an acid function, their agriculturally useful derivatives, such as amides, esters and thioesters.
To broaden the activity spectrum and to obtain synergistic effects, 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 heteroaryloxyphenoxypropionic esters, phenylacetic acid and its derivatives, 2-phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides, uracils and also phenylpyrazolines and isoxazolines and their derivatives.
Moreover, it may be useful to apply the compounds I alone or in combination with other herbicides or else also mixed with further crop protection agents, jointly, for example with compositions for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions which are employed for alleviating nutritional and trace element deficiencies. Other additives such as nonphytotoxic oils and oil concentrates may also be added.
Examples of herbicides which can be used in combination with the pyridine compounds of the formula I according to the present invention are:
b1 ) from the group of the lipid biosynthesis inhibitors:
alloxydim, alloxydim-sodium, butroxydim, clethodim, clodinafop, clodinafop- propargyl, cycloxydim, cyhalofop, cyhalofop-butyl, diclofop, diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop- butyl, fluazifop-P, fluazifop-P-butyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P- tefuryl, sethoxydim, tepraloxydim, tralkoxydim, benfuresate, butylate, cycloate, dalapon, dimepiperate, EPTC, esprocarb, ethofumesate, flupropanate, molinate, orbencarb, pebulate, prosulfocarb, TCA, thiobencarb, tiocarbazil, triallate and vernolate;
b2) from the group of the ALS inhibitors:
amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, bispyribac, bispyribac-sodium, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cloransulam, cloransulam-methyl, cyclosulfamuron, diclosulam, ethametsulfuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, florasulam, flucarbazone, flucarbazone-sodium, flucetosulfuron, flumetsulam, flupyrsulfuron, flupyrsulfuron- methyl-sodium, foramsulfuron, halosulfuron, halosulfuron-methyl, imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, mesosulfuron, metosulam, metsulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, penoxsulam, primisulfuron, primisulfuron-methyl, propoxycarbazone,
propoxycarbazone-sodium, prosulfuron, pyrazosulfuron, pyrazosulfuron-ethyl, pyribenzoxim, pyrimisulfan, pyriftalid, pyriminobac, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium, pyroxsulam, rimsulfuron, sulfometuron, sulfometuron-methyl, sulfosulfuron, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron- methyl, triasulfuron, tribenuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron, triflusulfuron-methyl and tritosulfuron;
b3) from the group of the photosynthesis inhibitors:
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-ethyl, prometon, prometryn, propanil, propazine, pyridafol, pyridate, siduron, simazine, simetryn, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutryn, thidiazuron and trietazine;
b4) from the group of the protoporphyrinogen-IX oxidase inhibitors:
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, thidiazimin, 2-chloro-5-[3,6- dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1 (2H)-pyrimidinyl]-4-fluoro-N-[(isopropyl)- methylsulfamoyl]benzamide (H-1 ; CAS 372137-35-4), ethyl [3-[2-chloro-4-fluoro-5-(1 - methyl-6-trifluoromethyl-2,4-dioxo-1 ,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2- pyridyloxy]acetate (H-2; CAS 353292-31 -6), N-ethyl-3-(2,6-dichloro-4-trifluoro- methylphenoxy)-5-methyl-1 H-pyrazole-1 -carboxamide (H-3; CAS 452098-92-9), N-tetrahydrofurfuryl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1 H-pyrazole-1 - carboxamide (H-4; CAS 915396-43-9), N-ethyl-3-(2-chloro-6-fluoro-4-trifluoromethyl- phenoxy)-5-methyl-1 H-pyrazole-1 -carboxamide (H-5; CAS 452099-05-7) and
N-tetrahydrofurfuryl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1 H- pyrazole-1 -carboxamide (H-6; CAS 45100-03-7);
b5) from the group of the bleacher herbicides:
aclonifen, amitrol, beflubutamid, benzobicyclon, benzofenap, clomazone,
diflufenican, fluridone, flurochloridone, flurtamone, isoxaflutole, mesotrione,
norflurazon, picolinafen, pyrasulfutole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, topramezone, 4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6- (trifluoromethyl)-3-pyridyl]carbonyl]bicyclo[3.2.1 ]oct-3-en-2-one (H-7; CAS 352010-68- 5) and 4-(3-trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl)pyrimidine (H-8; CAS 180608-33-7);
b6) from the group of the EPSP synthase inhibitors:
glyphosate, glyphosate-isopropylammonium and glyphosate-trimesium (sulfosate); b7) from the group of the glutamine synthase inhibitors:
bilanaphos (bialaphos), bilanaphos-sodium, glufosinate and glufosinate-ammonium; b8) from the group of the DHP synthase inhibitors:
asulam;
b9) from the group of the mitose 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;
b10) from the group of the VLCFA inhibitors:
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;
Compounds of the formula 2:
Figure imgf000048_0001
in which the variables have the following meanings:
Y is phenyl or 5- or 6-membered heteroaryl as defined at the outset, which radicals may be substituted by one to three groups Raa; R21,R22,R23,R24 are H, halogen or Ci-C4-alkyl; X is O or NH; N is 0 or 1 .
Compounds of the formula 2 have in particular the following meanings:
Figure imgf000048_0002
where # denotes the bond to the skeleton of the molecule; and
R2i i R22 R23 R24 are H i C!i F or CH3; R25 is halogen, Ci-C4-alkyl or Ci-C4-haloalkyl; R26 is Ci-C4-alkyl; R27 is halogen, Ci-C4-alkoxy or Ci-C4-haloalkoxy; R28 is H, halogen, Ci-C4-alkyl, Ci-C4-haloalkyl or Ci-C4-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:
Figure imgf000048_0003
R21 is H; R22,R23 are F; R24 is H or F; X is oxygen; N is 0 or 1 .
Particularly preferred compounds of the formula 2 are:
3-[5-(2,2-difluoroethoxy)-1 -methyl-3-trifluoromethyl-1 H-pyrazol-4-ylmethane- sulfonyl]-4-fluoro-5,5-dimethyl-4,5-dihydroisoxazole (2-1 ); 3-{[5-(2,2-difluoro- ethoxy)-1 -methyl-3-trifluoromethyl-1 H-pyrazol-4-yl]fluoromethanesulfonyl}-5,5-dimethyl- 4,5-dihydroisoxazole (2-2); 4-(4-fluoro-5,5-dimethyl-4,5-dihydroisoxazole-3-sulfonyl- methyl)-2-methyl-5-trifluoromethyl-2H-[1 ,2,3]triazole (2-3); 4-[(5,5-dimethyl-4,5- dihydroisoxazole-3-sulfonyl)fluoromethyl]-2-methyl-5-trifluoromethyl-2H-[1 ,2,3]triazole (2-4); 4-(5,5-dimethyl-4,5-dihydroisoxazole-3-sulfonylmethyl)-2-methyl-5-trifluoro- methyl-2H-[1 ,2,3]triazole (2-5); 3-{[5-(2,2-difluoroethoxy)-1 -methyl-3-trifluoromethyl-1 H- pyrazol-4-yl]difluoromethanesulfonyl}-5,5-dimethyl-4,5-dihydroisoxazole (2-6); 4-[(5,5-dimethyl-4,5-dihydroisoxazole-3-sulfonyl)difluoro
methyl-2H-[1 ,2,3]triazole (2-7); 3-{[5-(2,2-difluoroethoxy)-1 -methyl-3-trifluoromethyl-1 H- pyrazol-4-yl]difluoromethanesulfonyl}-4-fluoro-5,5-dimethyl-4,5-dihydroisoxazole (2-8); 4-[difluoro-(4-fluoro-5,5-dimethyl-4,5-dihydroisoxazole-3-sulfonyl)methyl]-2-methyl-5- trifluoromethyl-2H-[1 ,2,3]triazole (2-9);
b1 1 ) from the group of the cellulose biosynthesis inhibitors:
chlorthiamid, dichlobenil, flupoxam and isoxaben;
b12) from the group of the decoupler herbicides:
dinoseb, dinoterb and DNOC and its salts;
b13) from the group of the auxin herbicides:
2,4-D and its salts and esters, 2,4-DB and its salts and esters, aminopyralid and its salts such as aminopyralid-tris(2-hydroxypropyl)ammonium and its esters, benazolin, benazolin-ethyl, chloramben and its salts and esters, clomeprop, clopyralid and its salts and esters, dicamba and its salts and esters, dichlorprop and its salts and esters, dichlorprop-P and its salts and esters, fluroxypyr, fluroxypyr-butometyl, fluroxypyr- meptyl, MCPA and its salts and esters, MCPA-thioethyl, MCPB and its salts and esters, mecoprop and its salts and esters, mecoprop-P and its salts and esters, picloram and its salts and esters, quinclorac, quinmerac, TBA (2,3,6) and its salts and esters, triclopyr and its salts and esters, and 5,6-dichloro-2-cyclopropyl-4-pyrimidinecarboxylic acid (H-9; CAS 858956-08-8) and its salts and esters;
b14) from the group of the auxin transport inhibitors: diflufenzopyr, diflufenzopyr- sodium, naptalam and naptalam-sodium;
b15) from the group of the other herbicides: bromobutide, chlorflurenol, chlorflurenol- methyl, cinmethylin, cumyluron, dalapon, dazomet, difenzoquat, difenzoquat- metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, etobenzanid, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flurenol, flurenol-butyl, flurprimidol, fosamine, fosamine-ammonium, indanofan, maleic hydrazide, mefluidide, metam, methyl azide, methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine, triaziflam, tridiphane and 6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinol (H-10; CAS 499223-49-3) and its salts and esters.
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. 1 , Wiley VCH, 2007 and the literature quoted therein. 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 comprising 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. In binary compositions comprising at least one compound of the formula I as component A and at least one herbicide B, 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.
In binary compositions comprising at least one compound of the formula I as component A and at least one safener C, 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.
In ternary compositions comprising both at least one compound of the formula I as component A, at least one herbicide B and at least one safener C, 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 ; and 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 . Preferably, 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.
Moreover, they have reduced toxicity and are tolerated well by the plants.

Claims

Claims
1 . A tricyclic compound of the formula I
Figure imgf000052_0001
in which the variables have the following meaning:
R1 is 0-RA, S(0)n-RA or 0-S(0)n-RA;
RA is hydrogen, Ci-C4-alkyl, Z-Cs-Ce-cycloalkyl, Ci-C4-haloalkyl,
C2-C6-alkenyl, Z-C3-C6-cycloalkenyl, C2-C6-alkynyl, Z-(tri-Ci-C4-alkyl)silyl, Z-C(=0)-Ra, Z-NRi-C(0)-NR'Rii, Z-P(=0)(Ra)2, NR'R", a 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, which may be partially or fully substituted by groups Ra and/or Rb and which is attached via carbon or nitrogen,
Ra is hydrogen, OH, d-Cs-alkyl, Ci-C4-haloalkyl, Z-C3-C6-cyclo- alkyl, C2-Cs-alkenyl, Z-Cs-Ce-cycloalkenyl, C2-Cs-alkynyl, Z-Ci-C6-alkoxy, Z-Ci-C4-haloalkoxy, Z-Cs-Cs-alkenyloxy,
Z-Cs-Cs-alkynyloxy, NR'R", Ci-C6-alkylsulfonyl, Z-(tri-Ci-C4- 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, 4 or 5 groups R^
R', R" independently of one another are hydrogen, Ci-Cs-alkyl,
Ci-C4-haloalkyl, Cs-Cs-alkenyl, Cs-Cs-alkynyl, Z-C3-C6-cyclo- alkyl, Z-Ci-C8-alkoxy, Z-Ci-C8-haloalkoxy, Z-C(=0)-Rb,
Z-phenyl, a 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 is attached via Z;
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 is 0, 1 or 2;
R2 is phenyl, naphthyl or a 5- or 6-membered monocyclic or 9- or 10- membered bicyclic aromatic 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 or 4 groups Rb; Rb independently of one another are Z-CN, Z-OH, Z-NO2, Z-halogen, Ci-Cs-alkyl, Ci-C4-haloalkyl, C2-C8-alkenyl, C2-C8-alkynyl,
Z-Ci-Cs-alkoxy, Z-d-Cs-haloalkoxy, Z-C3-Cio-cycloalkyl,
0-Z-C3-Cio-cycloalkyl, Z-C(=0)-Rbb, NR'R", Z-(tri-Ci-C4-alkyl)silyl, Z-phenyl and S(0)nRbb,
where Rbb is Ci-Cs-alkyl or Ci-C6-haloalkyl and
n is 0, 1 or 2;
Rb together with the group Rb 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-Rc, one or two of these groups being N;
Rc is hydrogen or one of the groups mentioned for Rb;
R3, R4 independently of one another are a group Rc or the two groups
together are a double bond;
W, U independently of one another are N and C-Rc;
where in the groups Z, R1, R2, Rc and their subsubstituents, the carbon chains and/or the cyclic groups may be partially or fully substituted by groups Rb, or an N-oxide or an agriculturally suitable salt thereof.
The compound of the formula I according to claim 1 which corresponds to the formula 1.1
Figure imgf000053_0001
in which Rc1, Rc2, Rc3, Rc4 and Rc5 each correspond to a group Rc.
3. The compound according to claim 2 in which Rc1, Rc2, Rc3, Rc4 and Rc5 are each hydrogen.
The compound of the formula I according to claim 1 which corresponds to the formula 1.2
Figure imgf000054_0001
in which Rc1, Rc2, Rc3 and Rc4 each correspond to a group Rc.
The compound according to claim 4 in which Rc1, Rc2, Rc3 and Rc4 are each hydrogen.
The compound of the formula I according to claim 1 which corresponds to the formula 1.6
Figure imgf000054_0002
in which Rc1, Rc2, Rc3, Rc4 and Rc5 each correspond to a group Rc.
The compound according to claim 6 in which Rc1, Rc2, Rc3, Rc4 and Rc5 are each hydrogen.
The compound of the formula I according to claim 1 which corresponds to the formula 1.7
Figure imgf000054_0003
in which Rc1, Rc2, Rc3 and Rc4 each correspond to a group Rc.
9. The compound according to claim 8 in which Rc1, Rc2, Rc3 and Rc4 are each hydrogen.
10. The compound of the formula I according to any of claims 1 to 9 which
corresponds to the formula I .A
Figure imgf000055_0001
in which R5 and R6 are groups Rb and m is zero or an integer from one to four.
1 1 . The compound according to any of claims 2 to 9 in which
R1 is OH, OCHs, OC(0)CH3, OC(0)CH2CH3, OC(0)CH(CH3)2, OC(0)C(CH3)3, OC(0)-c-C3H5, OC(0)-C6H5, OC(0)-CH2C6H5, OC(0)CH2CI, OC(0)-CF3, OC(0)-CH2OCH3, OC(0)-N(CH3)2 or OC(0)-OCH2CH3;
R2 is phenyl which is substituted by a group selected from the group consisting of 2-Br, 2-CI, 2,4-CI2, 2-CI-4-F, 2-CI-5-F, 2-CI-6-F, 2-CI-4-CF3, 2-CI-5-CF3, 2-CI-6-CF3, 2-CI-3,6-F2, 2-F, 2,4-F2, 2,5-F2, 2,6-F2, 2-F-4-CF3, 2-F-5-CF3, 2-F-6-CF3, 2,3,6-F3, 2-N02, 2-N02-4-F, 2-N02-5-F, 2-N02-6-F, 2-N02-4- CF3, 2-N02-5-CF3, 2-N02-6-CF3, 2-N02-3,6-F2, 2-CN, 2-CH3, 2-CH3-4-F, 2-CH3-5-F, 2-CH3-6-F, 2-CH3-4-CF3, 2-CH3-5-CF3, 2-CH3-6-CF3, 2-CH3-3,6-
F2, 2-OCH3, 2-OCH3-4-F, 2-OCH3-5-F, 2-OCH3-6-F, 2-OCH3-4-CF3, 2-OCH3-5-CF3, 2-OCH3-6-CF3, 2-OCH3-3,6-F2, 2-CHF2, 2-CHF2-4-F, 2-CHF2-5-F, 2-CHF2-6-F, 2-CHF2-4-CF3, 2-CHF2-5-CF3, 2-CHF2-6-CF3, 2-CHF2-3,6-F2, 2-CF3, 2-CF3-4-F, 2-CF3-5-F, 2-CF3-6-F, 2-CF3-4-CF3, 2-CF3-5-CF3, 2-CF3-6-CF3, 2-CF3-3,6-F2, 2-OCHF2, 2-OCHF2-4-F,
2-OCHF2-5-F, 2-OCHF2-6-F, 2-OCHF2-4-CF3, 2-OCHF2-5-CF3, 2-OCHF2-6- CF3, 2-OCHF2-3,6-F2, 2-OCF3, 2-OCF3-4-F, 2-OCF3-5-F, 2-OCF3-6-F, 2-OCF3-4-CF3, 2-OCF3-5-CF3, 2-OCF3-6-CF3 and 2-OCF3-3,6-F2.
12. A composition comprising a herbicidally effective amount of at least one
compound of the formula I or an agriculturally suitable salt thereof according to any of claims 1 to 1 1 and auxiliaries customary for formulating crop protection agents.
13. The composition according to claim 12 which comprises at least one further active compound.
14. The composition according to claim 12 or 13 which comprises two further active compounds from the group of the herbicides and/or safeners.
15. 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 thereof according to any of claims 1 to 1 1 to act on plants, their seed and/or their habitat.
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Publication number Priority date Publication date Assignee Title
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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