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EP2379503A1 - Heterocyclic diketone derivatives with herbicidal action - Google Patents

Heterocyclic diketone derivatives with herbicidal action

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Publication number
EP2379503A1
EP2379503A1 EP09765101A EP09765101A EP2379503A1 EP 2379503 A1 EP2379503 A1 EP 2379503A1 EP 09765101 A EP09765101 A EP 09765101A EP 09765101 A EP09765101 A EP 09765101A EP 2379503 A1 EP2379503 A1 EP 2379503A1
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EP
European Patent Office
Prior art keywords
alkyl
formula
compounds
groups
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09765101A
Other languages
German (de)
French (fr)
Inventor
Dschun Song
Julia Major
Johannes Hutzler
Trevor William Newton
Thomas Ehrhardt
Klaus Kreuz
Klaus Grossmann
Robert Reinhard
Anja Simon
Ricarda Niggeweg
Bernd Sievernich
Matthias Witschel
William Karl Moberg
Liliana Parra Rapado
Tao QU
Frank Stelzer
Andrea Vescovi
Thomas Seitz
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BASF SE
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BASF SE
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Priority to EP09765101A priority Critical patent/EP2379503A1/en
Publication of EP2379503A1 publication Critical patent/EP2379503A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/65—One oxygen atom attached in position 3 or 5
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • C07D213/71—Sulfur atoms to which a second hetero atom is attached
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/18—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/20—Nitrogen atoms

Definitions

  • the present invention relates to heterocyclic compounds of the formula
  • R is hydrogen, Ci -C 6 -alkyl, C 4 haloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 -alkyl kinyl, Z-Cs-do-cycloalkyl, Ci-Ce-alkoxy-Ci -Ce-alkyl, C 1 -C 6 -cyanoalkyl, Z-phenyl,
  • ZC ( O) -R a2 , Z-SO 2 R 32 and tri-C 1 -C 4 -alkylsilyl;
  • R a2 is C 1 -C 6 -alkyl, C 1 -C 4 -haloalkyl, Z-C 1 -C 6 -alkoxy, Z-C 1 -C 4 -haloalkoxy and
  • Z is a covalent bond or C 1 -C 4 -alkylene;
  • R 1 , R "independently of one another are hydrogen, C 1 -C 8 -alkyl, C 1 -C 4 -haloalkyl, C 3 -C 8 -
  • R 1 and R may also together with the N-atom to which they are attached form a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic heterocycle containing 1, 2, 3 or 4 heteroatoms selected from O, N and S;
  • R 2 is phenyl, naphthyl or and 5- or 6-membered monocyclic or 9- or 10-membered bicyclic aromatic heterocycle containing 1, 2, 3 or 4 heteroatoms selected from O, N and S, wherein the cyclic groups unsubstituted or by 1, 2, 3, 4 or 5 groups R a are substituted, means;
  • R a can also form, together with the group R a attached to the adjacent carbon atom , a five- or six-membered saturated, partially or completely unsaturated ring which, in addition to carbon, 1, 2 or 3 heteroatoms, is selected from O, N and S. may contain;
  • X0 S or NR
  • YR 1 or NH-R
  • WO or S
  • A, E, G, MN and CR c wherein one or two groups thereof are N, R c is hydrogen or one of the groups mentioned in R a ; where in groups R 1 , R 2 , R 3 and their sub-substituents, the carbon chains and / or the cyclic groups may be partially or completely substituted by groups R a , and their N-oxides and agriculturally suitable salts.
  • the invention relates to processes and intermediates for the preparation of the compounds of formula I and their N-oxides, their agriculturally useful salts, as well as active ingredient combinations containing them, agents containing them and their use as herbicides, i. for controlling harmful plants, and a method for controlling undesired plant growth, comprising allowing a herbicidally effective amount of at least one compound of formula I or an agriculturally useful salt of I to act on plants, their seeds and / or their habitat.
  • An object of the present invention is to provide compounds having herbicidal activity.
  • active ingredients should be made available which have a high herbicidal action, in particular even at low application rates, and their compatibility with crop plants for commercial exploitation is sufficient.
  • the compounds according to the invention can be prepared by standard methods of organic chemistry, for example according to the following synthesis route:
  • This reaction is usually carried out at temperatures of -78 0 C to 12O 0 C, preferably -2O 0 C to 5O 0 C, in an inert organic solvent in the presence of a base (see Greene's Protective Groups in Organic Synthesis, Wiley).
  • 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, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and dimethyl sulfoxide, dimethylformamide and dimethylacetamide, more preferably halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene.
  • ethers
  • Bases are generally 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 alkali metal hydrogencarbonates such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides such as methylmagnesium chloride and alkali metal and alkaline earth metal alkoxides such as sodium, sodium, potassium, potassium tert-butoxide and Dimethoxymagnesium, also organic bases, eg tertiary amines such as trimethylamine, triethylamine, tributylamine, di-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration. Preference is given to alkali metal and alkaline earth metal hydrides, particularly preferably sodium hydride.
  • the bases are generally used in catalytic
  • the starting materials are generally reacted with one another in equimolar amounts.
  • Suitable solvents are water, alcohols such as methanol, ethanol, isopropanol, 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 like
  • Bases are generally 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 alkali metal hydrogencarbonates such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyl lithium and phenyl lithium, alkylmagnesium halides such as methylmagnesium chloride and also alkali metal and alkaline earth metal alcoholates.
  • alkali metal and alkaline earth metal hydroxides such as lithium hydro
  • te as sodium methoxide, sodium ethoxide, potassium, potassium tert-butoxide and Dimethoxymagnesium
  • organic bases such as tertiary amines such as tri- thylamine, triethylamine, tributylamine, di-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration.
  • tertiary amines such as tri- thylamine, triethylamine, tributylamine, di-isopropylethylamine and N-methylpiperidine
  • pyridine substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration.
  • the bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.
  • the compounds of the formula IVa are activated by introducing a leaving group L 1 .
  • Suitable leaving groups L 1 are generally those groups which increase the electrophilicity of the carbonyl group, for example O-alkyl, O-aryl, halides, activated esters or aldehydes (such as, for example, Weinreb amide), in particular pentafluorophenoxy.
  • This reaction is usually carried out at temperatures from -78 0 C to 12O 0 C, preferably -2O 0 C to 5O 0 C, in an inert organic solvent in the presence of a base such as. Triethylamine (see J. Agric and Food Chem., 1994, 42 (4), 1019-1025), a catalyst such as e.g. B. Dicyclohexylcarbodiimide (see Egyptian Journal of Chemistry 1994, 37 (3), 273-282) or other known coupling reagents.
  • a base such as. Triethylamine (see J. Agric and Food Chem., 1994, 42 (4), 1019-1025)
  • a catalyst such as e.g. B. Dicyclohexylcarbodiimide (see Egyptian Journal of Chemistry 1994, 37 (3), 273-282) or other known coupling reagents.
  • 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, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and dimethyl sulfoxide, dimethylformamide and dimethylacetamide, more preferably methylene chloride and toluene.
  • aromatic hydrocarbons such as toluene, o-,
  • Bases generally include 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, calcite 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 alkali metal hydrogencarbonates such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides such as methylmagnesium chloride and alkali metal and alkaline earth metal alkoxides such as sodium, sodium, potassium, potassium tert-butoxide and Dimethoxymagnesium, also organic bases, eg tertiary amines such as trimethylamine, triethylamine, tributylamine, di-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration.
  • organometallic compounds in particular alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, al
  • alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate, calcium carbonate, cesium carbonate and rubidium carbonate.
  • the bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.
  • agent HL 1 are alcohols, optionally subst. Phenols, N, O-dialkylhydroxylamine, in particular pentafluorophenol or N, O-dimethylhydroxylamine in question.
  • This reaction is usually carried out at temperatures of from -78 ° C to 120 0 C, preferably from -20 0 C to 50 0 C, in an inert organic solvent in the presence of a base or a Lewis acid or a catalyst [cf.. Bioorganic & Medicinal Chemistry (2004) Vol. 12 (6), 1357-1366].
  • 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, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably acetonitrile and dimethylformamide.
  • aliphatic hydrocarbons such as pentane, he
  • Suitable bases are generally 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 hydrogencarbonates such as sodium bicarbonate, organometallic compounds, especially alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides such as methylmagnesium chloride and alkali metal and alkaline
  • tertiary amines such as trimethylamine, triethylamine, tributylamine, di-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration.
  • alkali metal and alkaline earth metal alkoxides particularly preferably potassium tert-butoxide.
  • the bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.
  • the starting materials are generally reacted with one another in equimolar amounts.
  • the compounds of the formula I ' can be liberated by cleavage of the protective group from the compounds of the formula VII.
  • the reaction conditions depend on the nature of the protecting group SG; the splitting off of a possibly subst. Benzyl group succeeds z. B. with trifluoroacetic acid at temperatures of -78 0 C 0 C to 100 ° C, preferably -20 0 C to 50 ° C, in an inert organic solvent [cf. Greene's Protective Groups in Organic Synthesis, Wiley].
  • the tautomer 2 of the compounds of the formula I can be alkylated, acylated or sulfonated by reaction with an alkylating, acylating or sulfonating agent of the formula VIII by generally known methods.
  • R v is C -C 8 -alkyl, C 8-alkylcarbonyl, Ci-C8-Al kylsulfonyl, d- C ⁇ -Arylcarbonyl, Ci-C 8 -Arylsulfonyl, wherein the AI kyl, or aryl groups may be partially or completely substituted by groups R a , and L is a nucleophilic leaving group, such as halogen, alkoxy, alkyl or arylcarbonyloxy Acylating or sulfonating agents are in particular acetyl chloride, pivaloyl chloride, tosyl chloride or methylsulfonyl chloride in question.
  • the reaction mixtures are worked up in the usual way, e.g. by mixing with water, separation of the phases and optionally chromatographic purification of the crude products.
  • the intermediate and end products are z.T. in the form of colorless or slightly brownish, viscous oils which are freed from volatile constituents under reduced pressure and at moderately elevated temperature. If the intermediate and end products are obtained as solids, the purification can also be carried out by recrystallization or trituration.
  • isomer mixtures are obtained in the synthesis, separation is generally not necessary since the individual isomers may partially interconvert during preparation for use or during use (eg, under the action of light, acid or base). Corresponding transformations may also take place after application, for example in the treatment of plants in the treated plant or in the harmful plant to be controlled.
  • organic hydrocarbon moieties such as alkyl, halo (gen) alkyl, alkenyl, alkynyl, and the alkyl moieties and alkenyl moieties in alkoxy, halo (gen) are all collective groups for the substituents of the compounds of the invention.
  • halogenated substituents preferably carry one to five identical or different halogen atoms, in particular fluorine atoms or chlorine atoms.
  • alkyl and the alkyl moieties are, for example, alkoxy, alkylamino, dialkylamino, N-alkylsulfonylamino, 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 C atoms, for example 1 to 2, 1 to 4, or 1 to 6 carbon atoms, for example C 1 -C 6 -alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropy
  • Haloalkyl also referred to as haloalkyl: an alkyl radical as mentioned above whose hydrogen atoms are partially or fully substituted by halogen atoms such as fluorine, chlorine, bromine and / or iodine, for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl , Dichlorofluoro-methyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-di-fluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro -2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoro
  • Cycloalkyl and the cycloalkyl moieties for example, in cycloalkoxy or cycloalkylcarbonyl: monocyclic, saturated hydrocarbon groups having three or more C atoms, e.g. 3 to 6 carbon ring members such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • Alkenyl and 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. Atoms, z. 2 to 4, 2 to 6 or 3 to 6 carbon atoms and a double bond in any position, e.g.
  • 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-1
  • Cycloalkenyl monocyclic, monounsaturated hydrocarbon groups having 3 to 6, preferably 5 to 6 carbon ring members, such as cyclopenten-1-yl, cyclopentene-3-yl, cyclohexen-1-yl, cyclohexen-3-yl, cyclohexen-4-yl ,
  • Alkynyl and 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 , z. B. 2 to 4, 2 to 6, or 3 to 6 carbon atoms and a triple bond in any position, for.
  • C 2 -C 6 -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
  • Alkoxy alkyl, as defined above, which is bonded via an oxygen atom: z.
  • 5- or 6-membered heterocycle a cyclic group having 5 or 6 ring atoms wherein 1, 2, 3 or 4 ring atoms are heteroatoms selected from O, S and N, the cyclic group being saturated, partially unsaturated or aromatic is.
  • heterocyclic groups are.
  • the compounds of the formula I can contain one or more further chiral centers.
  • the compounds according to the invention can therefore be present as pure enantiomers or diastereomers or as mixtures of enantiomers or diastereomers.
  • the invention relates to both the pure enantiomers or diastereomers and mixtures thereof.
  • the compounds of the formula I can also be present in the form of the N-oxides and / or their agriculturally useful salts, the type of salt generally not being important.
  • the salts of those cations or the acid addition salts of those acids come into consideration whose cations, or anions, do not adversely affect the herbicidal activity of the compounds I.
  • the cations used are in particular ions of the alkali metals, preferably lithium, sodium or potassium, the alkaline earth metals, preferably calcium or magnesium, and the transition metals, preferably manganese, copper, zinc or iron. It is likewise possible to use ammonium as cation, in which case, if desired, one to four hydrogen atoms are represented by C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, hydroxyC 1 -C 4 -alkyl.
  • alkoxy-C 1 -C 4 -alkyl phenyl or benzyl, preferably ammonium, dimethylammonium, diisopropylammonium, 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 (C 1 -C 4 -alkyl) sulfonium or sulfoxonium ions, preferably tri (C 1 -C 4 -alkyl) sulfoxonium.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate,
  • variables of the compounds of the formula I have the following meanings, these being considered both individually and in combination with one another in particular embodiments of the compounds of the formula I:
  • a group of A, E, G and M is N.
  • A is N and E, G and M are CR a . These compounds correspond to the formula 1.1,
  • W is preferably O and the groups R a2 , R a3 and R a4 each correspond to a group R a and preferably have the following meanings: R a2 H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H, Br, OH and OCH 3 ;
  • R a3 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, especially H
  • R a4 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H.
  • a and M are N and E and G are CR a .
  • W is preferably O and the groups R a2 and R a3 each correspond to a group R a and preferably have the following meanings: R a2 H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H, Br, OH and
  • R a3 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H.
  • R 1 is alkoxy, in particular methoxy.
  • Phenyl such as C 6 H 5 , 4-CH 3 -C 6 H 4 , 4-FC 6 H 4 or S (O) n -R N , where R N is C 1 -C 6 -haloalkyl, such as CH 2 CF 3 , CH 2 CHF 2 .
  • R 2 is phenyl which is unsubstituted or partially or completely substituted by groups R a .
  • Particularly preferred are those compounds in which a group R a is in the ortho position.
  • Such compounds of the formula I are described by the formula I.A .:
  • R 5 and R 6 are groups R a as defined above, preferably halogen, NO 2 , C 1 -C 4 -alkyl, C 1 -C 2 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 2 -haloalkoxy.
  • a group R 6 is preferably in position 5.
  • X is O. In another embodiment, X is S. In another embodiment, X is NR.
  • Y is OH. In a further embodiment Y stands for SH. In a further embodiment Y stands for NHR.
  • W is O. In another embodiment, W is S.
  • Another preferred embodiment is represented by the compounds of the formula I which are derived from the tautomer 2; they correspond to the formula IT.
  • R v is preferably Ci-Cs-alkylcarbonyl, Ci-Cs-alkylsulfonyl, Ci-Cs-arylcarbonyl, or d-Cs-arylsulfonyl, wherein the alkyl or aryl groups may be partially or completely substituted by groups R a .
  • Aryl is preferably phenyl. Especially preferred are C 1 -C 5 -alkylcarbonyl and C 1 -C 8 -alkylsulfonyl, for example acetyl, pivaloyl, tosyl or methylsulfonyl.
  • 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 obtainable by quaternization of the pyridine nitrogen atom, which can preferably be effected by alkylation or arylation of the compounds of the formula I.
  • preferred salts of the compounds are the N-alkyl, in particular the N-methyl, or the N-phenyl salts.
  • Table 7 Compounds of the formula I in which X is O, Y is NH-CH (CH 3) 2 and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for each compound corresponds to one row of Table A.
  • Table 8 Compounds of the formula I in which X is O, Y is NH-CH (CH 3) 2 and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for each compound corresponds to one row of Table A.
  • Table 17 Compounds of the formula I in which X is S, Y is NH-C 2 H 5 and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for each compound corresponds to one row of Table A.
  • the compounds I and their agriculturally useful salts are suitable - both as mixtures of isomers and in the form of pure isomers - as herbicides. They are suitable as such or as appropriately formulated agent.
  • the compounds I in particular the preferred embodiments thereof, or agents containing them can be used in a further number of crop plants for the removal of undesirable plants.
  • the following cultures may be considered: Allium cepa, pineapple comosus, Arachis hypogaea, Asparagus officinalis, Avena sativa, Beta vulgaris spec. altissima, Beta vulgaris spec. rapeseed, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var.
  • crops also includes those that have been modified by breeding, mutagenesis or genetic engineering methods. Genetically engineered plants are plants whose genetic material has been altered in a way that does not occur under natural conditions by crossing, mutations or natural recombination (i.e., rearrangement of genetic information). As a rule, one or more genes are integrated into the genome of the plant in order to improve the properties of the plant.
  • crops thus also encompasses plants which, by breeding and genetic engineering measures, tolerate certain herbicide classes, such as
  • HPPD Hydroxyphenylpyruvate dioxygenase
  • ALS acetolactate synthase
  • sulfonylureas EP-A 257 993, US 5,013,659
  • imidazolium none see eg 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)
  • EPSPS enolpyruvylshikimate-3-phosphate synthase
  • Glyphosate see, for example, WO 92/00377), glutamine synthetase (GS) inhibitors such as. Glufosinate (see eg EP-A 242 236, EP-A 242 246) or oxynil herbicides (see eg US 5,559,024).
  • GS glutamine synthetase
  • crops thus also includes plants that use genetic engineering measures one or more toxins, eg. As those from the bacterial strain Bacillus ssp., Produce.
  • Toxins produced by such genetically engineered plants include e.g. Insecticidal proteins of Bacillus spp., In particular B. thuringiensis such as the endotoxins CrylAb, CrylAc, CrylF, Cry1Fe2, Cry2Ab, Cry3A, Cry3Bb1, Cry9c, Cry34Ab1 or Cry35Ab1; or vegetative insecticidal proteins (VIPs), e.g.
  • VIPs vegetative insecticidal proteins
  • VIP1, VIP2, VIP3, or VIP3A insecticidal proteins of nematode-colonizing bacteria, e.g. B. Photorhabdus spp. or Xenorhabdus spp .; Toxins from animal organisms, eg. B. Wepsen, spider or scorpion toxins; fungal toxins, e.g. B. from streptomycetes; herbal lectins, e.g. From pea or barley; agglutinins; Proteinase inhibitors, e.g. Trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; Ribosome Inactivating Proteins (RIPs), e.g. Ricin, corn RIP, abrin, luffin, saporin or bryodin; Steroid metabolizing
  • RIPs Ribosome Inactivating Proteins
  • Enzymes e.g. 3-hydroxysteroid oxidase, ecdysteroid IDP glycosyltransferase, cholesterol oxidase, ecdysone inhibitors or HMG-CoA reductase; ion channel blocker, e.g. B. inhibitors of sodium or calcium channels; Juvenile hormone esterase; Receptors for the diuretic hormone (helicokinin receptors); Stilbene synthase, bibenzyl synthase, chitinases and glucanases. These toxins can also be produced in the plants as proteoxins, hybrid proteins, 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 described in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878,
  • the methods for producing these genetically modified plants are known in the art and z. As set forth in the publications mentioned above. Many of the aforementioned toxins confer on the plants that produce them a tolerance to pests of all taxonomic arthropod classes, in particular to beetles (Coeleropta), diptera (Diptera) and butterflies (Lepidoptera) and nematodes (Nematoda). Genetically engineered plants that produce one or more genes encoding insecticidal toxins, e.g. As described in the publications mentioned above and partly commercially available, such as. B.
  • YieldGard ® (corn cultivars producing the toxin CrylAb), YieldGard ® Plus (corn cultivars producing the toxins CrylAb and Cry3Bb1), StarLink ® (corn cultivars producing the toxin Cry9c), Herculex ® RW (corn cultivars toxins which Cry34Ab1, Cry35Ab1 and the enzyme phosphinothricin N-acetyltransferase [PAT] produce); NuCOTN ® 33B (cotton cultivars producing the toxin CrylAc), Bollgard ® I (cotton cultivars producing the toxin CrylAc), Bollgard ® Il (cotton cultivars producing the toxins CrylAc and Cry2Ab2); VIPCOT ® (cotton varieties that produce a VIP toxin); NewLeaf ® (potato cultivars producing the Cry3A toxin); Bt Xtra ®, NatureGard® ®, KnockOut ®, Bit
  • crops thus also includes plants that produce by genetic engineering measures one or more proteins that cause increased resistance or resistance to bacterial, viral or fungal pathogens, such as.
  • PR proteins pathogenesis-related proteins
  • resistance proteins eg, potato varieties that produce two resistance genes against Phytophthora infestans from the Mexican wild potato Solanum bulbocastanum
  • T4 lysozyme z. Potato varieties resistant to bacteria such as Erwinia amylvora by the production of this protein).
  • crops thus also includes plants whose productivity has been improved by means of genetic engineering methods by z.
  • yield eg biomass, grain yield, starch, oil or protein content
  • crops also includes plants whose ingredients have been modified in particular to improve the human or animal diet using genetic engineering methods by z.
  • oil plants can produce health-promoting long-chain omega-3 fatty acids or monounsaturated omega-9 fatty acids (eg Nexera ® oilseed rape).
  • crops also includes plants that have been modified for the improved production of raw materials by means of genetic engineering methods by z. B.
  • amylopectin content of potatoes (Amflora ® potato) was increased. 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, come into consideration.
  • compositions for the desiccation and / or defoliation of plants, processes for the preparation of these agents and methods for the desiccation and / or defoliation of plants with the compounds of formula I have been found.
  • the compounds of formula I are particularly suitable for dehydration of the aerial parts of crop plants such as potato, oilseed rape, sunflower and soybean but also cereals. This enables a completely mechanical harvesting of these important crops.
  • harvest facilitation which is made possible by the time-concentrated dropping or reducing the adhesion of the tree to citrus fruit, olives or other types and varieties of pome, stone and peel fruit.
  • the same mechanism i.e. promoting the formation of release webs between fruit or leaf and shoot part of the plants, is also essential for a well controllable defoliation of crops, especially cotton.
  • shortening the time interval in which each cotton plant ripens leads to increased fiber quality after harvest.
  • the compounds I or the herbicidal compositions containing them for example in the form of directly sprayable aqueous solutions, powders, suspensions, even high-percentage aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents or granules by spraying , Misting, dusting, scattering, pouring or treatment of the seed or mixing with the seed.
  • the forms of application depend on the intended use; In any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • the herbicidal compositions contain a herbicidally effective amount of at least one compound of the formula I or an agriculturally useful salt of I and auxiliaries customary for the formulation of pesticides.
  • auxiliaries are preferred auxiliaries, solid carriers, surface-active substances (such as dispersants, protective colloids, emulsifiers, wetting agents and adhesives), organic and inorganic thickeners, bactericides, antifreeze agents, defoamers, if necessary, dyes and for seed formulations adhesives.
  • surface-active substances such as dispersants, protective colloids, emulsifiers, wetting agents and adhesives
  • organic and inorganic thickeners such as bactericides, antifreeze agents, defoamers, if necessary, dyes and for seed formulations adhesives.
  • thickeners ie, compounds which impart modified flowability to the formulation, ie, high-level at low viscosity and low viscosity in the agitated state
  • polysaccharides such as xanthan gum (Kelzan® from Kelco), Rhodopol® 23 (Rhone Poulenc) or Veegum ® (RT Vanderbilt) and organic and inorganic layer minerals such as Attaclay® (Engelhardt).
  • 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 may be added to stabilize the aqueous herbicidal formulation.
  • bactericides are bactericides based on diclorophene and benzyl alcohol hemiformal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas) and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acticide MBS der Fa. Thor Chemie)
  • antifreeze agents are ethylene glycol, propylene glycol, urea or glycerol.
  • colorants are both water-insoluble pigments and water-soluble dyes. Examples which may be mentioned under the names rhodamine B, Cl. Pigment Red 112 and Cl. Solvent Red 1 known dyes, and 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: 1, 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 polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose.
  • Suitable inert additives are, for example:
  • Mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, eg. As amines such as N-methylpyrrolidone or water.
  • amines such as N-methylpyrrolidone or water.
  • Solid carriers are mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour
  • alkali alkaline earth
  • ammonium salts of aromatic sulfonic acids eg lignosulfonic acids (eg Borrespers types, Borregaard), phenolsulfonic acids, naphthalenesulfonic acids (Morwet types , Akzo Nobel) and dibutylnaphthalenesulfonic acid (Nekal types, BASF SE)
  • fatty acids alkyl and alkylaryl sulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octa- decanols and also of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of na
  • Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.
  • Granules, e.g. Coating, impregnation and homogeneous granules can be prepared by binding the active compounds to solid carriers.
  • Aqueous application forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • the compounds of the formula I or Ia as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agents, tackifiers, dispersants or emulsifiers.
  • concentrates consisting of active substance, wetting, adhesion, dispersing or emulsifying agent and possibly solvent or oil, which are suitable for dilution with water.
  • concentrations of the compounds of the formula I in the ready-to-use formulations can be varied within wide limits.
  • the formulations generally contain from 0.001 to 98% by weight, preferably from 0.01 to 95% by weight, of at least one active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
  • the compounds I according to the invention can be formulated, for example, as follows:
  • active compound 15 parts by weight of active compound are dissolved in 75 parts by weight of an organic solvent (for example alkylaromatics) with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution in water results in an emulsion.
  • the formulation has 15% by weight active ingredient content.
  • active compound 25 parts by weight of active compound are dissolved in 35 parts by weight of an organic solvent (for example alkylaromatics) with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight).
  • organic solvent for example alkylaromatics
  • calcium dodecylbenzenesulfonate and castor oil ethoxylate in each case 5 parts by weight.
  • This mixture is added to water by means of an emulsifying machine (e.g., Ultraturax) in 30 parts by weight and made into a homogeneous emulsion. Dilution in water results in an emulsion.
  • the formulation has an active ingredient content of 25% by weight.
  • E Suspensions 20 parts by weight of active compound are comminuted with the addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent in a stirred ball mill to give a fine active substance suspension. Dilution in water results in a stable suspension of the active ingredient.
  • the active ingredient content in the formulation is 20% by weight.
  • F Water-dispersible and water-soluble granules 50 parts by weight of active compound are finely ground with the addition of 50 parts by weight of dispersing and wetting agents and prepared by means of industrial equipment (for example extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient.
  • the formulation has an active ingredient content of 50% by weight.
  • 0.5 parts by weight of active compound are finely ground and combined with 99.5 parts by weight of carriers. Common processes are extrusion, spray drying or the fluidized bed. This gives a granulate for direct application with 0.5 wt .-% active ingredient content.
  • the application of the compounds I or the herbicidal compositions containing them can take place in the pre-emergence, post-emergence or together with the seed of a crop. It is also possible to apply the herbicidal compositions or active ingredients characterized in that with the herbicidal agents or active ingredients pretreated seed of a crop plant is applied. If the active ingredients are less compatible with certain crops, then application techniques may be employed whereby the herbicidal agents are sprayed by the sprayers so as not to hit the leaves of the sensitive crops as far as possible, while the active ingredients affect the leaves underneath growing undesirable plants or the uncovered floor surface (post-directed, lay-by).
  • the application of the compounds of the formula I or of the herbicidal compositions can be carried out by treating seed.
  • the treatment of seed comprises essentially all techniques familiar to the skilled worker (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 according to the invention I or funds produced therefrom.
  • the herbicidal agents can be diluted or applied undiluted.
  • seed includes seeds of all kinds, e.g. Grains, seeds, fruits, tubers, cuttings and similar forms.
  • seed preferably describes grains and seeds here. Seeds of the abovementioned crops but also the seeds of transgenic or obtained by conventional breeding methods plants can be used as seeds.
  • the application rates of active ingredient are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (a. S.).
  • the compounds I are usually used in amounts of 0.001 to 10 kg per 100 kg of seed.
  • Safeners are chemical compounds that prevent or reduce damage to crops without significantly affecting the herbicidal activity of the compounds of formula I on undesirable plants. You can probably before sowing (for example in seed treatments, cuttings or seedlings) as well as in the pre or postemergence of the crop can be used.
  • the safeners and the compounds of formula I can be used simultaneously or sequentially.
  • Suitable safeners are, for example, (quinoline- ⁇ -oxy) acetic acids, 1-phenyl-5-haloalkyl-1H-1, 2,4-triazole-3-carboxylic acids, 1-phenyl-4,5-dihydro-5 alkyl-1H-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-benzoic acid amides, 1,8-naphthalic anhydride, 2-halo-4- (haloalkyl) -5-thiazolecarboxylic acids, phosphorothiolates and N-alkyl-O-phenylcarba
  • the compounds of formula I can be mixed with numerous representatives of other herbicidal or growth-regulating active ingredient groups or with safeners and applied together.
  • Bilanaphos (bialaphos), bilanaphos-sodium, glufosinate and glufosinate-ammonium; b8) from the group of DHP synthase inhibitors: asulam; b9) from the group of mitosis inhibitors:
  • Y is phenyl or 5- or 6-membered heteroaryl as defined above, which may be substituted by one to three groups R aa ; R 21 , R 22 , R 23 , R 24 are H, halogen, or C 1 -C 4 -alkyl; X is O or NH; n 0 or 1.
  • R 25 is halogen, C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl;
  • R 26 is C 1 -C 4 -alkyl;
  • R 27 is halogen, C 1 -C 4 -alkoxy or C 1 -C 4 -haloalkoxy;
  • R 28 is H, halogen, Ci-C 4 - alkyl, Ci-C 4 haloalkyl or Ci-C4-haloalkoxy;
  • m is 0, 1, 2 or 3;
  • Preferred compounds of the formula 2 have the following meanings: ', 3
  • MSMA oleic acid, oxaziclomefon, pelargonic acid, pyributicarb, quinoclamin, triaziflam, tridiphan and 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol (B-10; CAS 499223-49-3 ) and its salts and esters.
  • Examples of preferred safeners C are Benoxacor, Cloquintocet, Cyometrinil, Cyprusulfamide, Dichlormid, Dicyclonon, Dietholate, Fenchlorazole, Fenclorim, Flurazole, Fluxofenim, Furilazole, Isoxadifen, Mefenpyr, Mephenate, Naphthalic Anhydride, Oxabetrinile, 4- (Dichloroacetyl ) -1-oxa-4-azaspiro [4.5] decane (B-1 1; MON4660, CAS 71526-07-3) and 2,2,5-trimethyl-3- (dichloroacetyl) -1,3-oxazolidine (B -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, US Pat. B. The Compendium of Pesticide Common Names (http://www.alanwood.net/pesticides/); B. Hock, C. Fedtke, RR Schmidt, herbicides, Georg Thieme Verlag, Stuttgart 1995. Further herbicidal active compounds are known from WO 96/26202, WO 97/411 16, WO 97/41 117, WO 97/411 18, WO 01 / 83459 and WO 2008/074991 and W. Krämer et al. (ed.) "Modern Crop Protection Compounds", Vol. 1, Wiley VCH, 2007 and the literature cited therein.
  • the invention also relates to compositions in the form of a crop protection agent formulated as a 1-component composition
  • a crop protection agent formulated as a 1-component composition
  • a combination of active substances comprising at least one pyridine compound of the formula I and at least one further active ingredient, preferably selected from the active substances of groups b1 to b15, and at least one solid or liquid carrier and / or one or more surface-active substances and, if desired, one or more further auxiliaries customary for crop protection agents.
  • the invention also relates to compositions in the form of a plant 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 surface-active substances, and a second component containing at least one further active ingredient selected from the active compounds of groups b1 to b15, a solid or liquid carrier and / or one or more surface-active substances, wherein in addition both components may also contain other, customary for crop protection agents.
  • a plant 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 surface-active substances, and a second component containing at least one further active ingredient selected from the active compounds of groups b1 to b15, a solid or liquid carrier and / or one or more surface-active substances, wherein in addition both components may also contain other, customary for crop protection agents.
  • the weight ratio of the active compounds A: B is generally in the range from 1: 1000 to 1000: 1, preferably in the range from 1: 500 to 500: 1, in particular in the range of 1: 250 to 250: 1 and particularly preferably in the range of 1: 75 to 75: 1.
  • the weight ratio of the active compounds A: C is generally in the range from 1: 1000 to 1000: 1, preferably in the range from 1: 500 to 500: 1, in particular in the range of 1: 250 to 250: 1 and particularly preferably in the range of 1: 75 to 75: 1.
  • the relative proportions by weight of the components A: B are generally in the range from 1: 1000 to 1000: 1, preferably in the range of 1: 500 to 500: 1, in particular in the range of 1: 250 to 250: 1 and particularly preferably in the range of 1: 75 to 75: 1, the weight ratio of the component A: C usually in Range of 1: 1000 to 1000: 1, preferably in the range of 1: 500 to 500: 1, in particular in the range of 1: 250 to 250: 1 and more preferably in the range of 1: 75 to 75: 1, and the weight ratio of the components B: C, generally in the range from 1: 1000 to 1000: 1, preferably in the range from 1: 500 to 500: 1, in particular in the range from 1: 250 to 250: 1 and particularly preferably in the range from 1: 75 to 75: 1.
  • the weight ratio of components A + B to component C is preferably in the range from 1: 500 to 500: 1, in particular in the
  • compositions according to the invention containing in each case an individualized compound of the formula I and a mixing partner, or a mixture partner combination are given in the following Table B.
  • a further embodiment of the invention relates to the compositions B-1 to B-1237 listed in Table B, wherein in each case one row of Table B corresponds to a herbicidal composition comprising an individualized in the present specification compounds of formula I (component 1) and the further active ingredient from groups b1) to b15) and / or safener C (component 2) respectively indicated in the relevant line.
  • the active ingredients in the described compositions are each preferably present in synergistically effective amounts.
  • the compounds I and the compositions according to the invention may also have a plant-strengthening effect. They are therefore suitable for mobilizing plant-own defenses against infestation by undesirable microorganisms, such as harmful fungi, but also viruses and bacteria.
  • plant-strengthening (resistance-inducing) substances are to be understood as meaning those substances which are capable of stimulating the defense system of treated plants in such a way that they develop extensive resistance to these microorganisms during subsequent inoculation with undesired microorganisms.
  • the compounds I can be used to protect plants against attack by undesired microorganisms within a certain period of time after the treatment. The period within which protection is provided generally extends from 1 to 28 days, preferably 1 to 14 days after treatment of the plants with the compounds I or after treatment of the seed, up to 9 months after sowing.
  • the compounds I and the compositions according to the invention are also suitable for increasing crop yield.
  • Step 1 Methyl 3- (4-methoxy-benzyloxy) -pyridine-2-carboxylate A solution of 15.2 g of 3-hydroxy-pyridine-2-methyl ester in 200 ml of dimethylformamide (DMF) was admixed with 4 g NaH and stirred for 20 min -25 0 C stirred. Then, 15.4 g of para-methoxybenzyl chloride was added. The mixture was stirred at 40 ° C. for about 15 hours and then poured into water. After extraction with ethyl acetate, phase separation and washing of the combined organic phases with water and sat. NaCl solution, then drying and removal of the solvent, the residue was subjected to column chromatography. 20 g of the title compound were obtained as a yellow oil.
  • DMF dimethylformamide
  • Step 2 3- (4-Methoxy-benzyloxy) -pyridine-2-carboxylic acid
  • Step 3 3- (4-Methoxy-benzyloxy) -pyridine-2-carboxylic acid pentafluorophenyl ester
  • a solution of 5 g of the acid from Step 2 and 3.5 g of pentafluorophenol in 100 mL of CH 2 Cl 2 were added 2.4 g of N, N'-diisopropylcarbodiimide dropwise.
  • the mixture was stirred at 20-25 0 C for about 1 hr, then with sat. NaCl solution and concentrated in vacuo. After purification by column chromatography on the residue (petroleum ether: ethyl acetate 5: 1), 4.6 g of the title compound were obtained.
  • Step 4 Methyl 3- [3- (4-methoxy-benzyloxy) -pyridin-2-yl] -3-oxo-2- (2-trifluoromethyl-phenyl) -propionate
  • Step 5 3- (3-Hydroxy-pyridin-2-yl) -3-oxo-2- (2-trifluoromethyl-phenyl) -propionic acid methyl ester
  • the culture vessels used were plastic pots with loamy sand with about 3.0% humus as substrate.
  • the seeds of the test plants were sown separately by species.
  • the active ingredients suspended or emulsified in water were applied directly after sowing by means of finely distributing nozzles.
  • the jars were lightly rained to promote germination and growth and then covered with clear plastic hoods until the plants had grown. This cover causes a uniform germination of the test plants, if it was not affected by the active ingredients.
  • test plants were grown depending on the growth form only to a height of from 3 to 15 cm and then treated with the suspended or emulsified in water agents.
  • the test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and transplanted into the test containers a few days before the treatment.
  • the plants were kept species-specific at temperatures of 10 - 25 ° C and 20 - 35 ° C, respectively.
  • the trial period lasted for 2 to 4 weeks. During this time, the plants were cared for, and their response to each treatment was evaluated.
  • the rating was based on a scale of 0 to 100. 100 means no emergence of the plants or complete destruction of at least the above-ground parts and 0 no damage or normal growth course.
  • a good herbicidal activity is at values of at least 70 and a very good herbicidal activity is given at values of at least 85.
  • the plants used in the greenhouse experiments were composed of the following species:
  • the active ingredient 1-1 showed at a rate of 3.0 kg / ha in Iauf on against ABUTH a good and against SETIT a very good herbicidal action.
  • the active ingredient 1-17 showed at a rate of 1, 0 kg / ha postemergence against APESV a very good herbicidal activity.
  • the active compounds 1-1, and I-8 showed at a rate of 3.0 kg / ha postemergence against AVEFA a very good herbicidal activity. 7) The active ingredient 1-1 at an application rate of 0.25 kg / ha, the active ingredients I-
  • the active ingredient 1-17 showed at a rate of 1, 0 kg / ha postemergence against CHEAL a good herbicidal action.
  • the active ingredient 1-1 showed at a rate of 0.25 kg / ha postemergence against GALAP a very good herbicidal activity.

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Abstract

Heterocyclic compounds of the formula (I) in which the variables are defined according to the description, the agriculturally suitable salts thereof, processes and intermediates for preparing the compounds of the formula I, compositions comprising them and the use thereof as herbicides, i.e. for controlling harmful plants, and a method for controlling unwanted plant growth, in which a herbicidally active amount of at least one compound of the formula I is allowed to act on plants, the seeds thereof and/or the habitat thereof.

Description

HETEROZYKLISCHE DIKETON-DERIVATE MIT HERBIZIDER WIRKUNG HETEROCYCLIC DIKETONE DERIVATIVES WITH HERBICIDAL EFFECT
Beschreibungdescription
Die vorliegende Erfindung betrifft heterozyklische Verbindungen der FormelThe present invention relates to heterocyclic compounds of the formula
worin die Variablen folgende Bedeutung haben R1 OR, SR oder NR1R"; wherein the variables have the following meaning R 1 OR, SR or NR 1 R ";
R Wasserstoff, Ci -C6-Al kyl, Ci-C4-Haloalkyl, C2-C6-Alkenyl, C3-C6-Al kinyl, Z-Cs-do-Cycloalkyl, Ci-Ce-Alkoxy-Ci-Ce-alkyl, Ci-C6-Cyanoalkyl, Z-Phenyl,R is hydrogen, Ci -C 6 -alkyl, C 4 haloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 -alkyl kinyl, Z-Cs-do-cycloalkyl, Ci-Ce-alkoxy-Ci -Ce-alkyl, C 1 -C 6 -cyanoalkyl, Z-phenyl,
Z-C(=O)-Ra2, Z-SO2R32 und Tri-Ci-C4-alkylsilyl; Ra2 Ci-C6-Alkyl, Ci-C4-Haloalkyl, Z-Ci-C6-Alkoxy, Z-Ci-C4-Haloalkoxy undZC (= O) -R a2 , Z-SO 2 R 32 and tri-C 1 -C 4 -alkylsilyl; R a2 is C 1 -C 6 -alkyl, C 1 -C 4 -haloalkyl, Z-C 1 -C 6 -alkoxy, Z-C 1 -C 4 -haloalkoxy and
NRR";NRR ';
Z eine kovalente Bindung oder Ci-C4-Alkylen; R1, R" unabhängig voneinander Wasserstoff, d-Cs-Alkyl, Ci-C4-Haloalkyl, C3-C8-Z is a covalent bond or C 1 -C 4 -alkylene; R 1 , R "independently of one another are hydrogen, C 1 -C 8 -alkyl, C 1 -C 4 -haloalkyl, C 3 -C 8 -
Alkenyl, C3-C8-Al kinyl, Z-C3-C6-Cycloalkyl, Z-(C=O)-R32, Z-Ci-C8-Alkoxy, Z-Ci-Cs-Haloalkoxy;Alkenyl, C 3 -C 8 -alkyl kinyl, ZC 3 -C 6 cycloalkyl, Z- (C = O) -R 32, Z-C 8 alkoxy, Z-Ci-Cs-haloalkoxy;
R1 und R" können auch gemeinsam mit dem N-Atom, an das sie gebunden sind, einen 5- oder 6-gliedrigen monocyclischen oder 9- oder 10-gliedrigen bi- cyclischer Heterocyclus bilden, enthaltend 1 , 2, 3 oder 4 Heteroatome ausgewählt aus O, N und S;R 1 and R "may also together with the N-atom to which they are attached form a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic heterocycle containing 1, 2, 3 or 4 heteroatoms selected from O, N and S;
R2 Phenyl, Naphthyl oder und 5- oder 6-gliedriger monocyclischer oder 9- oder 10- gliedriger bicyclischer aromatischer Heterocyclus, enthaltend 1 , 2, 3 oder 4 Heteroatome ausgewählt aus O, N und S, wobei die cyclischen Gruppen unsubstitu- iert oder durch 1 , 2, 3 ,4 oder 5 Gruppen Ra substituiert sind, bedeutet;R 2 is phenyl, naphthyl or and 5- or 6-membered monocyclic or 9- or 10-membered bicyclic aromatic heterocycle containing 1, 2, 3 or 4 heteroatoms selected from O, N and S, wherein the cyclic groups unsubstituted or by 1, 2, 3, 4 or 5 groups R a are substituted, means;
Ra unabhängig voneinander Z-CN, Z-OH, Z-NO2, Z-Halogen, Ci-C8-Alkyl, d- C4-Haloalkyl, C2-C8-Al kenyl, C2-C8-Al kinyl, Z-Ci-C8-Alkoxy, Z-Ci-Cs-Haloalkoxy, Z-C3-Cio-Cycloalkyl, 0-Z-C3-Cio-Cycloalkyl, Z-C(=0)-Ra2, NRR", Z-(Tri-Ci-C4-alkyl)silyl, Z-Phenyl und S(O)nRbb, wobei Rbb Ci-Cβ-Alkyl, Ci-C6-Haloalkyl und Z-Phenyl bedeutet und n für O, 1 oder 2 steht;R a is independently Z-CN, Z-OH, Z-NO 2, Z is halogen, Ci-C 8 alkyl, d- C 4 haloalkyl, C 2 -C 8 -alkenyl, C 2 -C 8 - al kinyl, Z-C 8 alkoxy, Z-Ci-Cs-haloalkoxy, ZC 3 -Cio cycloalkyl, 0-ZC 3 -Cio cycloalkyl, ZC (= 0) -R a2, NRR ', Z (Tri-C 1 -C 4 -alkyl) silyl, Z-phenyl and S (O) n R bb , where R bb is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl and Z-phenyl and n is O, 1 or 2 stands;
Ra kann auch gemeinsam mit der an das benachbarte C-Atom gebundene Gruppe Ra einen fünf- oder sechsgliedrigen gesättigten, teilweise oder vollständig ungesättigten Ring bilden, der neben Kohlenstoff- 1 , 2 oder 3 Heteroatome ausge- wählt aus O, N und S enthalten kann;R a can also form, together with the group R a attached to the adjacent carbon atom , a five- or six-membered saturated, partially or completely unsaturated ring which, in addition to carbon, 1, 2 or 3 heteroatoms, is selected from O, N and S. may contain;
X O, S oder N-R; Y R1 oder NH-R; W O oder S;X0, S or NR; YR 1 or NH-R; WO or S;
A,E,G,M N und C-Rc, wobei eine oder zwei Gruppen davon N bedeuten, Rc Wasserstoff oder eine der bei Ra genannten Gruppen; wobei in Gruppen R1, R2, R3 und deren Untersubstituenten die Kohlenstoffketten und/oder die cyclischen Gruppen teilweise oder vollständig durch Gruppen Ra substituiert sein können, sowie deren N-Oxide und landwirtschaftlich geeignete Salze.A, E, G, MN and CR c , wherein one or two groups thereof are N, R c is hydrogen or one of the groups mentioned in R a ; where in groups R 1 , R 2 , R 3 and their sub-substituents, the carbon chains and / or the cyclic groups may be partially or completely substituted by groups R a , and their N-oxides and agriculturally suitable salts.
Außerdem betrifft die Erfindung Verfahren und Zwischenprodukte zur Herstellung der Verbindungen der Formel I und deren N-Oxide, deren landwirtschaftlich brauchbaren Salze, sowie sie enthaltende Wirkstoffkombinationen, sie enthaltende Mittel und deren Verwendung als Herbizide, d.h. zur Bekämpfung von Schadpflanzen, sowie ein Verfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs, bei dem man eine herbizid wirksame Menge mindestens einer Verbindung der Formel I oder eines landwirtschaftlich brauchbaren Salzes von I auf Pflanzen, deren Samen und/oder deren Lebensraum einwirken läßt. Weitere Ausführungsformen der vorliegenden Erfindung sind den Ansprüchen, der Beschreibung und den Beispielen zu entnehmen. Es versteht sich, dass die vorstehend genannten und die nachstehend noch zu erläuternden Merkmale des erfindungsgemäßen Gegenstandes nicht nur in der jeweils angegebenen Kombination, sondern auch in anderen Kombinationen verwendbar sind, ohne den Rahmen der Erfindung zu verlassen.In addition, the invention relates to processes and intermediates for the preparation of the compounds of formula I and their N-oxides, their agriculturally useful salts, as well as active ingredient combinations containing them, agents containing them and their use as herbicides, i. for controlling harmful plants, and a method for controlling undesired plant growth, comprising allowing a herbicidally effective amount of at least one compound of formula I or an agriculturally useful salt of I to act on plants, their seeds and / or their habitat. Further embodiments of the present invention can be taken from the claims, the description and the examples. It is understood that the features mentioned above and those yet to be explained of the subject matter according to the invention can be used not only in the particular combination specified, but also in other combinations, without departing from the scope of the invention.
Eine Aufgabe der vorliegenden Erfindung ist die Bereitstellung von Verbindungen mit herbizider Wirkung. Insbesondere sollen Wirkstoffe zur Verfügung gestellt werden, die eine hohe herbizide Wirkung, insbesondere bereits bei niedrigen Aufwandmengen, aufweisen und deren Verträglichkeit gegenüber Kulturpflanzen für eine kommerzielle Verwertung hinreichend ist.An object of the present invention is to provide compounds having herbicidal activity. In particular, active ingredients should be made available which have a high herbicidal action, in particular even at low application rates, and their compatibility with crop plants for commercial exploitation is sufficient.
Diese und weitere Aufgaben werden durch die eingangs definierten Verbindungen der Formel I und durch ihre N-Oxide, sowie deren landwirtschaftlich geeigneten Salze gelöst.These and other objects are achieved by the compounds of the formula I defined above and by their N-oxides, as well as their agriculturally suitable salts.
Die erfindungsgemäßen Verbindungen können nach Standardverfahren der organischen Chemie hergestellt werden, beispielsweise nach der folgenden Syntheseroute:The compounds according to the invention can be prepared by standard methods of organic chemistry, for example according to the following synthesis route:
Die Verbindungen der Formel I, in denen X für O oder S steht (=X1), und ihre Vorstufen, können in zwei tautomeren Formen vorliegen. Die Erfindung betrifft beide Tauto- mere. Nur der Übersichtlichkeit wegen wird in der Beschreibung meist nur ein Tauto- mer erwähnt.The compounds of formula I in which X is O or S (= X 1 ) and their precursors can exist in two tautomeric forms. The invention relates to both tautomers. For the sake of clarity, only one tautomer is mentioned in the description.
Tautomer 1 Tautomer 2 Carbonsäuren der Formel Il können mit Verbindungen der Formel III zu Verbindungen der Formel IV umgesetzt werden. In Formeln Il und III haben die Variablen die für Formel I angegebene Bedeutung. Die Gruppe R' steht für CrC4-AIkOXy, Y' für O oder S, HaI steht für ein Halogenatom oder eine andere geeignete nucleophile Abgangsgruppe, wie Alkoxy oder Phenoxy und SG bedeutet eine die Reaktivität von Y vermindernde Schutzgruppe, wie beispielsweise ggf. subst. Benzyl.Tautomer 1 tautomer 2 Carboxylic acids of the formula II can be reacted with compounds of the formula III to give compounds of the formula IV. In formulas II and III, the variables have the meaning given for formula I. The group R 'is CrC 4 -alkoxy, Y' is O or S, Hal is a halogen atom or another suitable nucleophilic leaving group, such as alkoxy or phenoxy, and SG is a protective group which reduces the reactivity of Y, for example optionally subst , Benzyl.
Diese Umsetzung erfolgt üblicherweise bei Temperaturen von -78 0C bis 12O0C, vorzugsweise -2O0C bis 5O0C, in einem inerten organischen Lösungsmittel in Gegenwart einer Base (vgl. Greene's Protective Groups in Organic Synthesis, Wiley).This reaction is usually carried out at temperatures of -78 0 C to 12O 0 C, preferably -2O 0 C to 5O 0 C, in an inert organic solvent in the presence of a base (see Greene's Protective Groups in Organic Synthesis, Wiley).
Geeignete Lösungsmittel sind aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Petrolether, aromatische Kohlenwasserstoffe wie Toluol, o-, m- und p- XyIoI, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorbenzol, Ether wie Diethylether, Diisopropylether, tert.-Butylmethylether, Dioxan, Anisol und Tetrahydrofuran, Nitrile wie Acetonitril und Propionitril, Ketone wie Aceton, Methylethyl- keton, Diethylketon und tert.-Butylmethylketon, sowie Dimethylsulfoxid, Dimethylform- amid und Dimethylacetamid, besonders bevorzugt halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorbenzol. Es können auch Gemische der genannten Lösungsmittel verwendet werden. Als Basen kommen allgemein anorganische Verbindungen wie Alkalimetall- und Erdalkalimetallhydroxide wie Lithiumhydroxid, Natriumhydroxid, Kaliumhydroxid und CaI- ziumhydroxid, Alkalimetall- und Erdalkalimetalloxide wie Lithiumoxid, Natriumoxid, CaI- ziumoxid und Magnesiumoxid, Alkalimetall- und Erdalkalimetallhydride wie Lithiumhydrid, Natriumhydrid, Kaliumhydrid und Calziumhydrid, Alkalimetallamide wie Lithium- amid, Natriumamid und Kaliumamid, Alkalimetall- und Erdalkalimetallcarbonate wieSuitable 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, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and dimethyl sulfoxide, dimethylformamide and dimethylacetamide, more preferably halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene. It is also possible to use mixtures of the solvents mentioned. Bases are generally 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
Lithiumcarbonat, Kaliumcarbonat und Calziumcarbonat sowie Alkalimetallhydrogencar- bonate wie Natriumhydrogencarbonat, metallorganische Verbindungen, insbesondere Alkalimetallalkyle wie Methyllithium, Butyllithium und Phenyllithium, Alkylmagnesiumha- logenide wie Methylmagnesiumchlorid sowie Alkalimetall- und Erdalkalimetallalkohola- te wie Natriummethanolat, Natriumethanolat, Kaliumethanolat, Kalium- tert.-Butanolat und Dimethoxymagnesium, außerdem organische Basen, z.B. tertiäre Amine wie Tri- methylamin, Triethylamin, Tributylamin, Di-isopropylethylamin und N-Methylpiperidin, Pyridin, substituierte Pyridine wie Collidin, Lutidin und 4-Dimethylaminopyridin sowie bicyclische Amine in Betracht. Bevorzugt werden Alkalimetall- und Erdalkalimetallhyd- ride, besonders bevorzugt Natriumhydrid. Die Basen werden im allgemeinen in kataly- tischen Mengen eingesetzt, sie können aber auch äquimolar, im Überschuß oder gegebenenfalls als Lösungsmittel verwendet werden.Lithium carbonate, potassium carbonate and calcium carbonate and alkali metal hydrogencarbonates such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides such as methylmagnesium chloride and alkali metal and alkaline earth metal alkoxides such as sodium, sodium, potassium, potassium tert-butoxide and Dimethoxymagnesium, also organic bases, eg tertiary amines such as trimethylamine, triethylamine, tributylamine, di-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration. Preference is given to alkali metal and alkaline earth metal hydrides, particularly preferably sodium hydride. The bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.
Die Edukte werden im allgemeinen in äquimolaren Mengen miteinander umgesetzt. The starting materials are generally reacted with one another in equimolar amounts.
Aus den Verbindungen der Formel IV wird die entsprechende Säure der Formel IVa freigesetzt. Diese Umsetzung erfolgt üblicherweise bei Temperaturen von -78 0C bis 12O0C, vorzugsweise -2O0C bis 5O0C, in einem inerten organischen Lösungsmittel in Gegenwart einer Base (vgl. Bioorganic and Medicinal Chemistry Letters (2006) Bd. 16(3), 718 - 721 ).From the compounds of formula IV, the corresponding acid of formula IVa is released. This reaction is usually carried out at temperatures from -78 0 C to 12O 0 C, preferably -2O 0 C and 5O 0 C, in an inert organic solvent in the presence of a base (see FIG. Bioorganic and Medicinal Chemistry Letters (2006) Vol. 16 ( 3), 718-721).
Geeignete Lösungsmittel sind Wasser, Alkohole wie Methanol, Ethanol, iso- Propanol, aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Pet- rolether, aromatische Kohlenwasserstoffe wie Toluol, o-, m- und p-Xylol, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorbenzol, Ether wieSuitable solvents are water, alcohols such as methanol, ethanol, isopropanol, 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 like
Diethylether, Diisopropylether, tert.-Butylmethylether, Dioxan, Anisol und Tetrahydrofu- ran, Nitrile wie Acetonitril und Propionitril, Ketone wie Aceton, Methylethylketon, Diethylketon und tert.-Butylmethylketon, sowie Dimethylsulfoxid, Dimethylformamid und Dimethylacetamid, besonders bevorzugt halogenierte Kohlenwasserstoffe wie Methy- lenchlorid, Chloroform und Chlorbenzol. Es können auch Gemische der genannten Lösungsmittel verwendet werden.Diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably halogenated hydrocarbons such as methyl lenchloride, chloroform and chlorobenzene. It is also possible to use mixtures of the solvents mentioned.
Als Basen kommen allgemein anorganische Verbindungen wie Alkalimetall- und Erdalkalimetallhydroxide wie Lithiumhydroxid, Natriumhydroxid, Kaliumhydroxid und CaI- ziumhydroxid, Alkalimetall- und Erdalkalimetalloxide wie Lithiumoxid, Natriumoxid, CaI- ziumoxid und Magnesiumoxid, Alkalimetall- und Erdalkalimetallhydride wie Lithiumhydrid, Natriumhydrid, Kaliumhydrid und Calziumhydrid, Alkalimetallamide wie Lithium- amid, Natriumamid und Kaliumamid, Alkalimetall- und Erdalkalimetallcarbonate wie Lithiumcarbonat, Kaliumcarbonat und Calziumcarbonat sowie Alkalimetallhydrogencar- bonate wie Natriumhydrogencarbonat, metallorganische Verbindungen, insbesondere Alkalimetallalkyle wie Methyllithium, Butyllithium und Phenyllithium, Alkylmagnesiumha- logenide wie Methylmagnesiumchlorid sowie Alkalimetall- und Erdalkalimetallalkohola- te wie Natriummethanolat, Natriumethanolat, Kaliumethanolat, Kalium- tert.-Butanolat und Dimethoxymagnesium, außerdem organische Basen, z.B. tertiäre Amine wie Tri- methylamin, Triethylamin, Tributylamin, Di-isopropylethylamin und N-Methylpiperidin, Pyridin, substituierte Pyridine wie Collidin, Lutidin und 4-Dimethylaminopyridin sowie bicyclische Amine in Betracht. Bevorzugt werden Alkalimetall- und Erdalkalimetallhydroxide besonders bevorzugt Lithiumhydroxid. Die Basen werden im allgemeinen in katalytischen Mengen eingesetzt, sie können aber auch äquimolar, im Überschuß oder gegebenenfalls als Lösungsmittel verwendet werden. Die Verbindungen der Formel IVa werden durch Einführung einer Abgangsgruppe L1 aktiviert. Als Abgangsgruppen L1 kommen allgemein solche Gruppen in Frage, die die Elektrophilie der Carbonylgruppe erhöhen, beispielsweise O-Alkyl, O-Aryl, Halogenide, aktivierte Ester oder Aldehyde (wie z. B. Weinreb-Amid), insbesondere Pentafluorphen- oxy. Bases are generally 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 alkali metal hydrogencarbonates such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyl lithium and phenyl lithium, alkylmagnesium halides such as methylmagnesium chloride and also alkali metal and alkaline earth metal alcoholates. te as sodium methoxide, sodium ethoxide, potassium, potassium tert-butoxide and Dimethoxymagnesium, also organic bases, such as tertiary amines such as tri- thylamine, triethylamine, tributylamine, di-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration. Preference is given to alkali metal hydroxides and alkaline earth metal hydroxides, particularly preferably lithium hydroxide. The bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent. The compounds of the formula IVa are activated by introducing a leaving group L 1 . Suitable leaving groups L 1 are generally those groups which increase the electrophilicity of the carbonyl group, for example O-alkyl, O-aryl, halides, activated esters or aldehydes (such as, for example, Weinreb amide), in particular pentafluorophenoxy.
Diese Umsetzung erfolgt üblicherweise bei Temperaturen von -78 0C bis 12O0C, vorzugsweise -2O0C bis 5O0C, in einem inerten organischen Lösungsmittel in Gegenwart einer Base wie z. B. Triethylamin (vgl. J. Agric. and Food Chem. 1994, 42(4), 1019 - 1025.), eines Katalysators wie z. B. Dicyclohexylcarbodiimid (vgl. Egyptian Journal of Chemistry 1994, 37(3), 273-282) oder anderer bekannter Kupplungsreagenzien.This reaction is usually carried out at temperatures from -78 0 C to 12O 0 C, preferably -2O 0 C to 5O 0 C, in an inert organic solvent in the presence of a base such as. Triethylamine (see J. Agric and Food Chem., 1994, 42 (4), 1019-1025), a catalyst such as e.g. B. Dicyclohexylcarbodiimide (see Egyptian Journal of Chemistry 1994, 37 (3), 273-282) or other known coupling reagents.
Geeignete Lösungsmittel sind aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Petrolether, aromatische Kohlenwasserstoffe wie Toluol, o-, m- und p- XyIoI, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorben- zol, Ether wie Diethylether, Diisopropylether, tert.-Butylmethylether, Dioxan, Anisol und Tetrahydrofuran, Nitrile wie Acetonitril und Propionitril, Ketone wie Aceton, Methylethyl- keton, Diethylketon und tert.-Butylmethylketon, sowie Dimethylsulfoxid, Dimethylform- amid und Dimethylacetamid, besonders bevorzugt Methylenchlorid und Toluol Es können auch Gemische der genannten Lösungsmittel verwendet werden. Als Basen kommen allgemein anorganische Verbindungen wie Alkalimetall- und Erdalkalimetallhydroxide wie Lithiumhydroxid, Natriumhydroxid, Kaliumhydroxid und Calzi- umhydroxid, Alkalimetall- und Erdalkalimetalloxide wie Lithiumoxid, Natriumoxid, Calzi- umoxid und Magnesiumoxid, Alkalimetall- und Erdalkalimetallhydride wie Lithiumhydrid, Natriumhydrid, Kaliumhydrid und Calziumhydrid, Alkalimetallamide wie Lithium- amid, Natriumamid und Kaliumamid, Alkalimetall- und Erdalkalimetallcarbonate wieSuitable 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, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and dimethyl sulfoxide, dimethylformamide and dimethylacetamide, more preferably methylene chloride and toluene. Mixtures of said solvents may also be used become. Bases generally include 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, calcite 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
Lithiumcarbonat, Kaliumcarbonat und Calziumcarbonat sowie Alkalimetallhydrogencar- bonate wie Natriumhydrogencarbonat, metallorganische Verbindungen, insbesondere Alkalimetallalkyle wie Methyllithium, Butyllithium und Phenyllithium, Alkylmagnesiumha- logenide wie Methylmagnesiumchlorid sowie Alkalimetall- und Erdalkalimetallalkohola- te wie Natriummethanolat, Natriumethanolat, Kaliumethanolat, Kalium- tert.-Butanolat und Dimethoxymagnesium, außerdem organische Basen, z.B. tertiäre Amine wie Tri- methylamin, Triethylamin, Tributylamin, Di-isopropylethylamin und N-Methylpiperidin, Pyridin, substituierte Pyridine wie Collidin, Lutidin und 4-Dimethylaminopyridin sowie bicyclische Amine in Betracht. Besonders bevorzugt werden Alkalimetall- und Erdalka- limetallcarbonate wie Lithiumcarbonat, Kaliumcarbonat, Calziumcarbonat, Cäsiumcar- bonat und Rubidiumcarbonat. Die Basen werden im allgemeinen in katalytischen Mengen eingesetzt, sie können aber auch äquimolar, im Überschuß oder gegebenenfalls als Lösungsmittel verwendet werden.Lithium carbonate, potassium carbonate and calcium carbonate and alkali metal hydrogencarbonates such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides such as methylmagnesium chloride and alkali metal and alkaline earth metal alkoxides such as sodium, sodium, potassium, potassium tert-butoxide and Dimethoxymagnesium, also organic bases, eg tertiary amines such as trimethylamine, triethylamine, tributylamine, di-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration. Particularly preferred are alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate, calcium carbonate, cesium carbonate and rubidium carbonate. The bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.
Die Edukte werden im allgemeinen in äquimolaren Mengen miteinander umgesetzt. Als Agenz H-L1 kommen Alkohole, ggf. subst. Phenole, N,O-Dialkylhydroxylamin, insbesondere Pentafluorphenol oder N,O-Dimethylhydroxylamin in Frage.The starting materials are generally reacted with one another in equimolar amounts. As agent HL 1 are alcohols, optionally subst. Phenols, N, O-dialkylhydroxylamine, in particular pentafluorophenol or N, O-dimethylhydroxylamine in question.
Die Verbindungen der Formel V werden mit Essigsäurederivaten der Formel VI zu den Verbindungen der Formel VII umgesetzt. The compounds of the formula V are reacted with acetic acid derivatives of the formula VI to give the compounds of the formula VII.
Diese Umsetzung erfolgt üblicherweise bei Temperaturen von -78°C bis 1200C, vorzugsweise -200C bis 500C, in einem inerten organischen Lösungsmittel in Gegenwart einer Base, bzw. einer Lewissäure oder eines Katalysators [vgl. Bioorganic & Medicinal Chemistry (2004) Bd. 12(6), 1357-1366].This reaction is usually carried out at temperatures of from -78 ° C to 120 0 C, preferably from -20 0 C to 50 0 C, in an inert organic solvent in the presence of a base or a Lewis acid or a catalyst [cf.. Bioorganic & Medicinal Chemistry (2004) Vol. 12 (6), 1357-1366].
Geeignete Lösungsmittel sind aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Petrolether, aromatische Kohlenwasserstoffe wie Toluol, o-, m- und p- XyIoI, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorbenzol, Ether wie Diethylether, Diisopropylether, tert.-Butylmethylether, Dioxan, Anisol und Tetrahydrofuran, Nitrile wie Acetonitril und Propionitril, Ketone wie Aceton, Methylethyl- keton, Diethylketon und tert.-Butylmethylketon, sowie Dimethylsulfoxid, Dimethylform- amid und Dimethylacetamid, besonders bevorzugt Acetonitril und Dimethylformamid Es können auch Gemische der genannten Lösungsmittel verwendet werden. Als Basen kommen allgemein anorganische Verbindungen wie Alkalimetall- und Er- dalkalimetallhydroxide wie Lithiumhydroxid, Natriumhydroxid, Kaliumhydroxid und CaI- ziumhydroxid, Alkalimetall- und Erdalkalimetalloxide wie Lithiumoxid, Natriumoxid, CaI- ziumoxid und Magnesiumoxid, Alkalimetall- und Erdalkalimetallhydride wie Lithiumhydrid, Natriumhydrid, Kaliumhydrid und Calziumhydrid, Alkalimetallamide wie Lithium- amid, Natriumamid und Kaliumamid, Alkalimetall- und Erdalkalimetallcarbonate wie Lithiumcarbonat, Kaliumcarbonat, Calziumcarbonat, Cäsiumcarbonat und Rubidium- carbonat sowie Alkalimetallhydrogencarbonate wie Natriumhydrogencarbonat, metallorganische Verbindungen, insbesondere Alkalimetallalkyle wie Methyllithium, Butylli- thium und Phenyllithium, Alkylmagnesiumhalogenide wie Methylmagnesiumchlorid sowie Alkalimetall- und Erdalkalimetallalkoholate wie Natriummethanolat, Natriumetha- nolat, Kaliumethanolat, Kalium- tert.-Butanolat und Dimethoxymagnesium, außerdem organische Basen, z.B. tertiäre Amine wie Trimethylamin, Triethylamin, Tributylamin, Di-isopropylethylamin und N-Methylpiperidin, Pyridin, substituierte Pyridine wie Collidin, Lutidin und 4-Dimethylaminopyridin sowie bicyclische Amine in Betracht. Bevorzugt werden Alkalimetall- und Erdalkalimetallalkoholate, besonders bevorzugt Kalium- tert- Butanolat.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, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably acetonitrile and dimethylformamide. Mixtures of the solvents mentioned can also be used. Suitable bases are generally 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 hydrogencarbonates such as sodium bicarbonate, organometallic compounds, especially alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides such as methylmagnesium chloride and alkali metal and alkaline earth metal alkoxides such as sodium methoxide, sodium ethanate, potassium ethanolate, potassium tert-butoxide and dimethoxy magnesium, as well as organic Bases, e.g. tertiary amines such as trimethylamine, triethylamine, tributylamine, di-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration. Preference is given to alkali metal and alkaline earth metal alkoxides, particularly preferably potassium tert-butoxide.
Die Basen werden im allgemeinen in katalytischen Mengen eingesetzt, sie können aber auch äquimolar, im Überschuß oder gegebenenfalls als Lösungsmittel verwendet werden.The bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.
Die Edukte werden im allgemeinen in äquimolaren Mengen miteinander umgesetzt. The starting materials are generally reacted with one another in equimolar amounts.
Die Verbindungen der Formel I' können durch Abspalten der Schutzgruppe aus den Verbindungen der Formel VII freigesetzt werden. Die Reaktionsbedingungen hängen von der Natur der Schutzgruppe SG ab; die Abspaltung einer ggf. subst. Benzyl- gruppe gelingt z. B. mit Trifluoressigsäure bei Temperaturen von -780C0C bis 100°C, vorzugsweise -200C bis 50°C, in einem inerten organischen Lösungsmittel [vgl. Gree- ne's Protective Groups in Organic Synthesis, Wiley].The compounds of the formula I 'can be liberated by cleavage of the protective group from the compounds of the formula VII. The reaction conditions depend on the nature of the protecting group SG; the splitting off of a possibly subst. Benzyl group succeeds z. B. with trifluoroacetic acid at temperatures of -78 0 C 0 C to 100 ° C, preferably -20 0 C to 50 ° C, in an inert organic solvent [cf. Greene's Protective Groups in Organic Synthesis, Wiley].
Die Einführung der von Sauerstoff verschiedenen Gruppen X, bzw. Y in die Verbindungen der Formel I' , bzw. ihrer Vorstufen, erfolgt nach allgemein bekannten Metho- den.The introduction of the oxygen-different groups X, or Y into the compounds of the formula I 'or their precursors, takes place by generally known methods.
Das Tautomer 2 der Verbindungen der Formel I kann durch Umsetzung mit einem Alkylierungs-, Acylierungs- oder Sulfonierungsmittel der Formel VIII nach allgemein bekannten Methoden alkyliert, acyliert, bzw. sulfoniert werden.The tautomer 2 of the compounds of the formula I can be alkylated, acylated or sulfonated by reaction with an alkylating, acylating or sulfonating agent of the formula VIII by generally known methods.
X1H W R «_x' w X 1 HW R « _ x ' w
SA R Tauto 'mer 2 Vl" s.M MΛγ γ R2 IT In Formel VIII steht Rv für Ci -C8-Al kyl, Ci-C8-Alkylcarbonyl, Ci -C8-Al kylsulfonyl, d- Cβ-Arylcarbonyl, Ci-C8-Arylsulfonyl, wobei die AI kyl, bzw. Arylgruppen teilweise oder vollständig durch Gruppen Ra substituiert sein können, und L steht für eine nucleophile Abgangsgruppe, wie z.B. Halogen, Alkoxy, Alkyl- oder Arylcarbonyloxy. Als Acylierungs- oder Sulfonierungsmittel kommen insbesondere Acetylchlorid, Pivaloylchlorid, Tosylchlorid oder Methylsulfonylchlorid in Frage.SA Tauto R 'mer Vl 2 "s. M M Λ γ γ R 2 IT In formula VIII R v is C -C 8 -alkyl, C 8-alkylcarbonyl, Ci-C8-Al kylsulfonyl, d- Cβ-Arylcarbonyl, Ci-C 8 -Arylsulfonyl, wherein the AI kyl, or aryl groups may be partially or completely substituted by groups R a , and L is a nucleophilic leaving group, such as halogen, alkoxy, alkyl or arylcarbonyloxy Acylating or sulfonating agents are in particular acetyl chloride, pivaloyl chloride, tosyl chloride or methylsulfonyl chloride in question.
Die Reaktionsgemische werden in üblicher weise aufgearbeitet, z.B. durch Mischen mit Wasser, Trennung der Phasen und gegebenenfalls chromatographische Reinigung der Rohprodukte. Die Zwischen- und Endprodukte fallen z.T. in Form farbloser oder schwach bräunlicher, zäher Öle an, die unter vermindertem Druck und bei mäßig er- höhter Temperatur von flüchtigen Anteilen befreit oder gereinigt werden. Sofern die Zwischen- und Endprodukte als Feststoffe erhalten werden, kann die Reinigung auch durch Umkristallisieren oder Digerieren erfolgen.The reaction mixtures are worked up in the usual way, e.g. by mixing with water, separation of the phases and optionally chromatographic purification of the crude products. The intermediate and end products are z.T. in the form of colorless or slightly brownish, viscous oils which are freed from volatile constituents under reduced pressure and at moderately elevated temperature. If the intermediate and end products are obtained as solids, the purification can also be carried out by recrystallization or trituration.
Sofern einzelne Verbindungen I nicht auf den voranstehend beschriebenen Wegen zugänglich sind, können sie durch Derivatisierung anderer Verbindungen I hergestellt werden.If individual compounds I are not accessible in the above-described ways, they can be prepared by derivatization of other compounds I.
Sofern bei der Synthese Isomerengemische anfallen, ist im allgemeinen jedoch eine Trennung nicht unbedingt erforderlich, da sich die einzelnen Isomere teilweise während der Aufbereitung für die Anwendung oder bei der Anwendung (z.B. unter Licht-, Säureoder Baseneinwirkung) ineinander umwandeln können. Entsprechende Umwandlungen können auch nach der Anwendung, beispielsweise bei der Behandlung von Pflanzen in der behandelten Pflanze oder in der zu bekämpfenden Schadpflanze erfolgen.However, if isomer mixtures are obtained in the synthesis, separation is generally not necessary since the individual isomers may partially interconvert during preparation for use or during use (eg, under the action of light, acid or base). Corresponding transformations may also take place after application, for example in the treatment of plants in the treated plant or in the harmful plant to be controlled.
Die für die Substituenten der erfindungsgemäßen Verbindungen genannten organi- sehen Molekülteile stellen Sammelbegriffe für individuelle Aufzählungen der einzelnen Gruppenmitglieder dar. Sämtliche Kohlenwasserstoffketten, wie Alkyl, Halo(gen)alkyl, Alkenyl, Alkinyl, sowie die Alkylteile und Alkenylteile in Alkoxy, Halo(gen)alkoxy, Alkyl- amino, Dialkylamino, N-Alkylsulfonylamino, Alkenyloxy, Alkinyloxy, Alkoxyamino, Alkyl- aminosulfonylamino, Dialkylaminosulfonylamino, Alkenylamino, Alkinylamino, N-(Alke- nyl)-N-(alkyl)-amino, N-(Alkinyl)-N-(alkyl)-amino, N-(Alkoxy)-N-(alkyl)-amino, N-(Alke- nyl)-N-(alkoxy)-amino oder N-(Alkinyl)-N-(alkoxy)-amino können geradkettig oder verzweigt sein.All organic hydrocarbon moieties, such as alkyl, halo (gen) alkyl, alkenyl, alkynyl, and the alkyl moieties and alkenyl moieties in alkoxy, halo (gen) are all collective groups for the substituents of the compounds of the invention. alkoxy, 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.
Das Präfix Cn-Cm- gibt die jeweilige Kohlenstoffzahl der Kohlenwasserstoffeinheit an. Sofern nicht anders angegeben tragen halogenierte Substituenten vorzugsweise ein bis fünf gleiche oder verschiedene Halogenatome, insbesondere Fluoratome oder Chloratome.The prefix C n -Cm- indicates the respective carbon number of the hydrocarbon moiety. Unless otherwise stated, halogenated substituents preferably carry one to five identical or different halogen atoms, in particular fluorine atoms or chlorine atoms.
Die Bedeutung Halogen steht jeweils für Fluor, Chlor, Brom oder lod. Ferner bedeuten beispielsweise: Alkyl sowie die Alkylteile beispielsweise in Alkoxy, Alkylamino, Dialkylamino, N-Alkyl- sulfonylamino, Alkylaminosulfonylamino, Dialkylaminosulfonylamino, N-(Alkenyl)-N- (alkyl)-amino, N-(Alkinyl)-N-(alkyl)-amino, N-(Alkoxy)-N-(alkyl)-amino: gesättigte, ge- radkettige oder verzweigte Kohlenwasserstoffreste mit einem oder mehr C-Atomen, z.B. 1 bis 2, 1 bis 4, oder 1 bis 6 Kohlenstoffatomen, z.B. Ci-C6-Alkyl wie 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-Methylpen- tyl, 4-Methylpentyl, 1 ,1-Dimethylbutyl, 1 ,2-Dimethylbutyl, 1 ,3-Dimethylbutyl, 2,2-Di- methylbutyl, 2,3-Dimethylbutyl, 3,3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbutyl, 1 ,1 ,2-Tri- methylpropyl, 1 ,2,2-Trimethylpropyl, 1-Ethyl-1-methylpropyl, 1-Ethyl-2-methylpropyl. In einer erfindungsgemäßen Ausführungsform steht Alkyl für kleine Alkylgruppen wie d- C4-Alkyl. In einer anderen erfindungsgemäßen Ausführungsform steht Alkyl für größere Alkylgruppen wie Cs-Cβ-Alkyl.The meaning halogen in each case represents fluorine, chlorine, bromine or iodine. In addition, for example, alkyl and the alkyl moieties are, for example, alkoxy, alkylamino, dialkylamino, N-alkylsulfonylamino, 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 C atoms, for example 1 to 2, 1 to 4, or 1 to 6 carbon atoms, for example C 1 -C 6 -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-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2 Trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl. In one embodiment of the invention, alkyl is small alkyl groups such as C 1 -C 4 -alkyl. In another embodiment of the invention, alkyl is greater alkyl groups such as Cs-Cβ-alkyl.
Halogenalkyl (auch als Haloalkyl bezeichnet): einen Alkylrest wie vorstehend genannt, dessen Wasserstoffatome partiell oder vollständig durch Halogenatome wie Fluor, Chlor, Brom und/oder lod substituiert sind, z.B. Chlormethyl, Dichlormethyl, Tri- chlormethyl, Fluormethyl, Difluormethyl, Trifluormethyl, Chlorfluormethyl, Dichlorfluor- methyl, Chlordifluormethyl, 2-Fluorethyl, 2-Chlorethyl, 2-Bromethyl, 2-lodethyl, 2,2-Di- fluorethyl, 2,2,2-Trifluorethyl, 2-Chlor-2-fluorethyl, 2-Chlor-2,2-difluorethyl, 2,2-Dichlor- 2-fluorethyl, 2,2,2-Trichlorethyl, Pentafluorethyl, 2-Fluorpropyl, 3-Fluorpropyl, 2,2-Di- fluorpropyl, 2,3-Difluorpropyl, 2-Chlorpropyl, 3-Chlorpropyl, 2,3-Dichlorpropyl, 2-Brom- propyl, 3-Brompropyl, 3,3,3-Trifluorpropyl, 3,3,3-Trichlorpropyl, 2,2,3,3,3-Pentafluor- propyl, Heptafluorpropyl, 1-(Fluormethyl)-2-fluorethyl, 1-(Chlormethyl)-2-chlorethyl, 1- (Brommethyl)-2-bromethyl, 4-Fluorbutyl, 4-Chlorbutyl, 4-Brombutyl und Nonafluorbutyl.Haloalkyl (also referred to as haloalkyl): an alkyl radical as mentioned above whose hydrogen atoms are partially or fully substituted by halogen atoms such as fluorine, chlorine, bromine and / or iodine, for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl , Dichlorofluoro-methyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-di-fluoroethyl, 2,2,2-trifluoroethyl, 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-di-fluoropropyl, 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-pentafluoro - propyl, heptafluoropropyl, 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl and nonafluorobutyl.
Cycloalkyl sowie die Cycloalkylteile beispielsweise in Cycloalkoxy oder Cycloalkyl- carbonyl: monocyclische, gesättigte Kohlenwasserstoffgruppen mit drei oder mehr C- Atomen, z.B. 3 bis 6 Kohlenstoffringgliedern, wie Cyclopropyl, Cyclobutyl, Cyclopentyl und Cyclohexyl.Cycloalkyl and the cycloalkyl moieties, for example, in cycloalkoxy or cycloalkylcarbonyl: monocyclic, saturated hydrocarbon groups having three or more C atoms, e.g. 3 to 6 carbon ring members such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
Alkenyl sowie Alkenylteile beispielsweise in Alkenylamino, Alkenyloxy, N-(Alkenyl)- N-(alkyl)-amino, N-(Alkenyl)-N-(alkoxy)-amino: einfach ungesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit zwei oder mehr C-Atomen, z. B. 2 bis 4, 2 bis 6 oder 3 bis 6 Kohlenstoffatomen und einer Doppelbindung in einer beliebigen Position, z.B. C2-C6-Alkenyl wie 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-but- enyl, 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-Di- methyl-2-propenyl, 1 ,2-Dimethyl-1-propenyl, 1 ,2-Dimethyl-2-propenyl, 1-Ethyl-1-prop- enyl, 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,Alkenyl and 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. Atoms, z. 2 to 4, 2 to 6 or 3 to 6 carbon atoms and a double bond in any position, e.g. 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-buteny 1, 2, 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-but- enyl, 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: monocyclische, einfach ungesättigte Kohlenwasserstoffgruppen mit 3 bis 6, vorzugsweise 5 bis 6 Kohlenstoffringgliedern, wie Cyclopenten-1-yl, Cyclopen- ten-3-yl, Cyclohexen-1-yl, Cyclohexen-3-yl, Cyclohexen-4-yl.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 to 6 carbon ring members, such as cyclopenten-1-yl, cyclopentene-3-yl, cyclohexen-1-yl, cyclohexen-3-yl, cyclohexen-4-yl ,
Alkinyl sowie Alkinylteile beispielsweise in Alkinyloxy, Alkinylamino, N-(Alkinyl)-N-(al- kyl)-amino oder N-(Alkinyl)-N-(alkoxy)-amino: geradkettige oder verzweigte Kohlenwasserstoffgruppen mit zwei oder mehr C-Atomen, z. B. 2 bis 4, 2 bis 6, oder 3 bis 6 Kohlenstoffatomen und einer Dreifachbindung in beliebiger Position, z. B. C2-C6-Alkinyl wie Ethinyl, 1-Propinyl, 2-Propinyl, 1-Butinyl, 2-Butinyl, 3-Butinyl, 1-Methyl-2-propinyl, 1-Pentinyl, 2-Pentinyl, 3-Pentinyl, 4-Pentinyl, 1-Methyl-2-butinyl, 1-Methyl-3-butinyl, 2-Methyl-3-butinyl, 3-Methyl-1 -butinyl, 1 ,1-Dimethyl-2-propinyl, 1 -Ethyl-2-propinyl, 1-Hexinyl, 2-Hexinyl, 3-Hexinyl, 4-Hexinyl, 5-Hexinyl, 1-Methyl-2-pentinyl, 1 -Methyl-3- pentinyl, 1-Methyl-4-pentinyl, 2-Methyl-3-pentinyl, 2-Methyl-4-pentinyl, 3-Methyl-1-pen- tinyl, 3-Methyl-4-pentinyl, 4-Methyl-1 -pentinyl, 4-Methyl-2-pentinyl, 1 ,1-Dimethyl-2-but- inyl, 1 ,1-Dimethyl-3-butinyl, 1 ,2-Dimethyl-3-butinyl, 2,2-Dimethyl-3-butinyl, 3,3-Dime- thyl-1-butinyl, 1-Ethyl-2-butinyl, 1 -Ethyl-3-butinyl, 2-Ethyl-3-butinyl, 1-Ethyl-1-methyl-2- propinyl.Alkynyl and 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 , z. B. 2 to 4, 2 to 6, or 3 to 6 carbon atoms and a triple bond in any position, for. C 2 -C 6 -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 thyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl.
Alkoxy: Alkyl, wie vorstehend definiert, das über ein O-Atom gebunden ist: z. B. Me- thoxy, Ethoxy, n-Propoxy, 1 -Methylethoxy, Butoxy, 1-Methylpropoxy, 2-Methylpropoxy oder 1 ,1-Dimethylethoxy, Pentoxy, 1-Methylbutoxy, 2-Methylbutoxy, 3-Methylbutoxy, 1 ,1-Dimethylpropoxy, 1 ,2-Dimethylpropoxy, 2,2-Dimethylpropoxy, 1-Ethylpropoxy, Hex- oxy, 1-Methylpentoxy, 2-Methylpentoxy, 3-Methylpentoxy, 4-Methylpentoxy, 1 ,1 -Di- methylbutoxy, 1 ,2-Dimethylbutoxy, 1 ,3-Dimethylbutoxy, 2,2-Dimethylbutoxy, 2,3-Di- methylbutoxy, 3,3-Dimethylbutoxy, 1-Ethylbutoxy, 2-Ethylbutoxy, 1 ,1 ,2-Trimethylprop- oxy, 1 ,2,2-Trimethylpropoxy, 1-Ethyl-1-methylpropoxy oder 1-Ethyl-2-methylpropoxy. 5- oder 6-gliedriger Heterocyclus: eine cyclische Gruppe, die 5 oder 6 Ringatome aufweist wobei 1 , 2, 3 oder 4 Ringatome Heteroatome sind, die ausgewählt sind aus O, S und N, wobei die cyclische Gruppe gesättigt, partiell ungesättigt oder aromatisch ist. Beispiele für heterocyclische Gruppen sind.Alkoxy: alkyl, as defined above, which is bonded via an oxygen atom: z. Methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1, 1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1, 1- Dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy, 1, 2 Dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 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. 5- or 6-membered heterocycle: a cyclic group having 5 or 6 ring atoms wherein 1, 2, 3 or 4 ring atoms are heteroatoms selected from O, S and N, the cyclic group being saturated, partially unsaturated or aromatic is. Examples of heterocyclic groups are.
Die Verbindungen der Formel I können, je nach Substitutionsmuster, ein oder mehrere weitere Chiralitätszentren enthalten. Die erfindungsgemäßen Verbindungen können daher als reine Enantiomere oder Diastereomere oder als Enantiomeren- oder Diastereomerengemische vorliegen. Gegenstand der Erfindung sind sowohl die reinen Enantiomeren oder Diastereomeren als auch deren Gemische.Depending on the substitution pattern, the compounds of the formula I can contain one or more further chiral centers. The compounds according to the invention can therefore be present as pure enantiomers or diastereomers or as mixtures of enantiomers or diastereomers. The invention relates to both the pure enantiomers or diastereomers and mixtures thereof.
Die Verbindungen der Formel I können auch in Form der N-Oxide und/oder ihrer landwirtschaftlich brauchbaren Salze vorliegen, wobei es auf die Art des Salzes in der Regel nicht ankommt. Im Allgemeinen kommen die Salze derjenigen Kationen oder die Säureadditionssalze derjenigen Säuren in Betracht, deren Kationen, beziehungsweise Anionen, die herbizide Wirkung der Verbindungen I nicht negativ beeinträchtigen.The compounds of the formula I can also be present in the form of the N-oxides and / or their agriculturally useful salts, the type of salt generally not being important. In general, the salts of those cations or the acid addition salts of those acids come into consideration whose cations, or anions, do not adversely affect the herbicidal activity of the compounds I.
Es kommen als Kationen insbesondere Ionen der Alkalimetalle, vorzugsweise Lithium, Natrium oder Kalium, der Erdalkalimetalle, vorzugsweise Calcium oder Magnesium, und der Übergangsmetalle, vorzugsweise Mangan, Kupfer, Zink oder Eisen in Betracht. Ebenso kann als Kation Ammonium verwendet werden, wobei hier gewünsch- tenfalls ein bis vier Wasserstoffatome durch Ci-C4-Alkyl, Hydroxy-Ci-C4-alkyl, C1-C4- Alkoxy-Ci-C4-alkyl, Hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, Phenyl oder Benzyl ersetzt sein können, vorzugsweise Ammonium, Dimethylammonium, Diisopropylammonium, Tetramethylammonium, Tetrabutylammonium, 2-(2-Hydroxyeth-1 -oxy)eth-1 -ylammonium, Di(2-hydroxyeth-1-yl)ammonium, Trimethylbenzylammonium. Als Ammoniumkation kommt auch das durch Alkylierung oder Arylierung quaternisierte Pyridin-Stickstoffatom der Formel I in Frage. Des Weiteren kommen Phosphoniumionen, Sulfoniumionen, vorzugsweise Tri(Ci-C4-alkyl)sulfonium oder Sulfoxoniumionen, vorzugsweise Tri(Ci- C4-alkyl)sulfoxonium, in Betracht. Anionen von brauchbaren Säureadditionsalzen sind in erster Linie Chlorid, Bromid, Fluorid, Hydrogensulfat, Sulfat, Dihydrogenphosphat, Hydrogenphosphat, Nitrat,The cations used are in particular ions of the alkali metals, preferably lithium, sodium or potassium, the alkaline earth metals, preferably calcium or magnesium, and the transition metals, preferably manganese, copper, zinc or iron. It is likewise possible to use ammonium as cation, in which case, if desired, one to four hydrogen atoms are represented by C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, hydroxyC 1 -C 4 -alkyl. alkoxy-C 1 -C 4 -alkyl, phenyl or benzyl, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2- (2-hydroxyeth-1-oxy) eth-1-ylammonium, di (2-hydroxyeth-1 -yl) ammonium, trimethylbenzylammonium. Also suitable as the ammonium cation is the pyridine nitrogen atom of the formula I quaternized by alkylation or arylation. Further suitable are phosphonium ions, sulfonium ions, preferably tri (C 1 -C 4 -alkyl) sulfonium or sulfoxonium ions, preferably tri (C 1 -C 4 -alkyl) sulfoxonium. Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate,
Hydrogencarbonat, Carbonat, Hexafluorosilikat, Hexafluorophosphat, Benzoat sowie die Anionen von Ci-C4-Alkansäuren, vorzugsweise Formiat, Acetat, Propionat, Butyrat oder Trifluoracetat.Hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate, butyrate or trifluoroacetate.
Die besonders bevorzugten Ausführungsformen der Zwischenprodukte in Bezug auf die Variablen entsprechen denen der Gruppen der Formel I.The particularly preferred embodiments of the intermediates with respect to the variables correspond to those of the groups of the formula I.
In einer besonderen Ausführungsform haben die Variablen der Verbindungen der Formel I folgende Bedeutungen, wobei diese sowohl für sich allein betrachtet als auch in Kombination miteinander besondere Ausgestaltungen der Verbindungen der Formel I darstellen:In a particular embodiment, the variables of the compounds of the formula I have the following meanings, these being considered both individually and in combination with one another in particular embodiments of the compounds of the formula I:
In einer bevorzugten Ausführungsform der Verbindungen der Formel I steht eine Gruppe aus A, E, G und M für N.In a preferred embodiment of the compounds of formula I, a group of A, E, G and M is N.
In einer bevorzugten Ausführungsform der Verbindungen der Formel I steht A für N und E, G und M stehen für C-Ra. Diese Verbindungen entsprechen der Formel 1.1 ,In a preferred embodiment of the compounds of formula I, A is N and E, G and M are CR a . These compounds correspond to the formula 1.1,
worin W bevorzugt für O steht und die Gruppen Ra2, Ra3 und Ra4 jeweils einer Gruppe Ra entsprechen und bevorzugt folgende Bedeutungen haben: Ra2 H, OH, CN, Halogen, Alkyl, Alkoxy, Haloalkyl, insbesondere H, Br, OH und OCH3; wherein W is preferably O and the groups R a2 , R a3 and R a4 each correspond to a group R a and preferably have the following meanings: R a2 H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H, Br, OH and OCH 3 ;
Ra3 H, OH, CN, Halogen, Alkyl, Alkoxy, Haloalkyl, insbesondere H; Ra4 H, OH, CN, Halogen, Alkyl, Alkoxy, Haloalkyl, insbesondere H.R a3 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, especially H; R a4 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H.
In einer weiteren bevorzugten Ausführungsform der Verbindungen der Formel I steht A und M für N und E und G stehen für C-Ra. Diese Verbindungen entsprechen der For¬In a further preferred embodiment of the compounds of the formula I, A and M are N and E and G are CR a . These compounds correspond to the For¬
worin W bevorzugt für O steht und die Gruppen Ra2 und Ra3 jeweils einer Gruppe Ra entsprechen und bevorzugt folgende Bedeutungen haben: Ra2 H, OH, CN, Halogen, Alkyl, Alkoxy, Haloalkyl, insbesondere H, Br, OH und wherein W is preferably O and the groups R a2 and R a3 each correspond to a group R a and preferably have the following meanings: R a2 H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H, Br, OH and
OCH3; Ra3 H, OH, CN, Halogen, Alkyl, Alkoxy, Haloalkyl, insbesondere H.OCH 3 ; R a3 is H, OH, CN, halogen, alkyl, alkoxy, haloalkyl, in particular H.
In einer ersten bevorzugten Ausführungsform der Erfindung steht R1 für Alkoxy, ins- besondere Methoxy. In einer weiteren bevorzugten Ausführungsform steht R für H, C-ι-C6-Alkyl, wie CH3, C2H5, n-C3H7, CH(CH3)2, n-C3H9, oder C(CH3)S; C3-C6-Cycloalkyl-Ci-C4-alkyl, wie Cyc- lopropylmethyl, C3-C6-Al kenyl, wie CH2CH=CH2, CH2C(CHs)=CH2, CH2CH2CH=CH2, CH2CH2C(CHs)=CH2, CH2CH2CH2CH=CH2, CH2CH2CH2C(CHs)=CH2, oder ggf. subst. Phenyl, wie C6H5, 4-CH3-C6H4, 4-F-C6H4 oder S(O)n-RN, worin RN für Ci-C6-Halogen- alkyl steht, wie CH2CF3, CH2CHF2.In a first preferred embodiment of the invention, R 1 is alkoxy, in particular methoxy. In a further preferred embodiment, R is H, C 1 -C 6 -alkyl, such as CH 3 , C 2 H 5 , nC 3 H 7 , CH (CH 3 ) 2, nC 3 H 9 , or C (CH 3 ) S; C 3 -C 6 -cycloalkyl-C 1 -C 4 -alkyl, such as cyclopropylmethyl, C 3 -C 6 -alkynyl, such as CH 2 CH = CH 2 , CH 2 C (CH 2) 2 (CH 2 ) 2 , CH 2 CH 2 CH = CH 2, CH 2 CH 2 C (CHs) = CH 2, CH 2 CH 2 CH 2 CH = CH 2, CH 2 CH 2 CH 2 C (CHs) = CH 2, or unsubstituted or substituted. Phenyl, such as C 6 H 5 , 4-CH 3 -C 6 H 4 , 4-FC 6 H 4 or S (O) n -R N , where R N is C 1 -C 6 -haloalkyl, such as CH 2 CF 3 , CH 2 CHF 2 .
In einer weiteren bevorzugten Ausgestaltung steht R2 für Phenyl, welches unsubsti- tuiert ist oder teilweise oder vollständig durch Gruppen Ra substituiert ist. Besonders bevorzugt sind solche Verbindungen, in denen eine Gruppe Ra in ortho-Position steht. Solche Verbindungen der Formel I werden durch die Formel I. A beschrieben:In a further preferred embodiment, R 2 is phenyl which is unsubstituted or partially or completely substituted by groups R a . Particularly preferred are those compounds in which a group R a is in the ortho position. Such compounds of the formula I are described by the formula I.A .:
In Formel I.A steht der Index m für eine ganze Zahl von Null bis vier, bevorzugt für 0, 1 oder 2, insbesondere for 0 oder 1. R5 und R6 stehen für Gruppen Ra, wie eingangs definiert, bevorzugt für Halogen, NO2, Ci-C4-Alkyl, Ci-C2-Halogenalkyl, Ci-C4-Alkoxy und Ci-C2-Halogenalkoxy. Eine Gruppe R6 steht bevorzugt in Position 5.In formula IA, the subscript m is an integer from zero to four, preferably 0, 1 or 2, in particular 0 or 1. R 5 and R 6 are groups R a as defined above, preferably halogen, NO 2 , C 1 -C 4 -alkyl, C 1 -C 2 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 2 -haloalkoxy. A group R 6 is preferably in position 5.
In einer bevorzugten Ausführungsform steht X für O. In einer weiteren Ausführungsform steht X für S. In einer weiteren Ausführungsform steht X für NR.In a preferred embodiment, X is O. In another embodiment, X is S. In another embodiment, X is NR.
In einer bevorzugten Ausführungsform steht Y für OH. In einer weiteren Ausführungsform steht Y für SH. In einer weiteren Ausführungsform steht Y für NHR.In a preferred embodiment, Y is OH. In a further embodiment Y stands for SH. In a further embodiment Y stands for NHR.
In einer bevorzugten Ausführungsform steht W für O. In einer weiteren Ausführungsform steht W für S.In a preferred embodiment, W is O. In another embodiment, W is S.
Eine weitere bevorzugte Ausführungsform stellen die Verbindungen der Formel I dar, welche von dem Tautomeren 2 abgeleitet sind; sie entsprechen der Formel IT .Another preferred embodiment is represented by the compounds of the formula I which are derived from the tautomer 2; they correspond to the formula IT.
Die besonders bevorzugten Ausführungsformen der Verbindungen der Formel IT in Bezug auf die Variablen entsprechen denen der Gruppen der Formel I.The particularly preferred embodiments of the compounds of the formula IT with respect to the variables correspond to those of the groups of the formula I.
Rv bedeutet bevorzugt Ci-Cs-Alkylcarbonyl, Ci-Cs-Alkylsulfonyl, C-i-Cs-Arylcarbonyl, oder d-Cs-Arylsulfonyl, wobei die Alkyl-, bzw. Arylgruppen teilweise oder vollständig durch Gruppen Ra substituiert sein können. Aryl bedeutet bevorzugt Phenyl. Besonders bevorzugt sind d-Cs-Alkylcarbonyl und Ci -Cs-Al kylsulfonyl, beispielsweise Acetyl, Pi- valoyl, Tosyl oder Methylsulfonyl.R v is preferably Ci-Cs-alkylcarbonyl, Ci-Cs-alkylsulfonyl, Ci-Cs-arylcarbonyl, or d-Cs-arylsulfonyl, wherein the alkyl or aryl groups may be partially or completely substituted by groups R a . Aryl is preferably phenyl. Especially preferred are C 1 -C 5 -alkylcarbonyl and C 1 -C 8 -alkylsulfonyl, for example acetyl, pivaloyl, tosyl or methylsulfonyl.
Eine weitere Ausführungsform betrifft die N-Oxide der Verbindungen der Formel I. Eine weitere Ausführungsform betrifft Salze der Verbindungen der Formel I, insbesondere solche erhältlich durch Quaternisierung des Pyridin-Stickstoffatoms, die bevorzugt erfolgen kann durch Alkylierung oder Arylierung der Verbindungen der Formel I. Entsprechend sind bevorzugte Salze der Verbindungen die N-Alkyl-, insbesondere die N-Methyl-, bzw. die N-Phenyl-Salze.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 obtainable by quaternization of the pyridine nitrogen atom, which can preferably be effected by alkylation or arylation of the compounds of the formula I. preferred salts of the compounds are the N-alkyl, in particular the N-methyl, or the N-phenyl salts.
Insbesondere sind im Hinblick auf ihre Verwendung die in den folgenden Tabellen zusammengestellten Verbindungen der Formel I, welche der Formel 1.1 A entsprechen, bevorzugt. Die in den Tabellen für einen Substituenten genannten Gruppen stellen außerdem für sich betrachtet, unabhängig von der Kombination, in der sie genannt sind, eine besonders bevorzugte Ausgestaltung des betreffenden Substituenten dar.In particular, with regard to their use, the compounds of the formula I compiled in the following tables, which correspond to the formula 1.1A, are preferred. The groups mentioned in the tables for a substituent are also considered individually, regardless of the combination in which they are mentioned, a particularly preferred embodiment of the substituent in question.
Tabelle 1Table 1
Verbindungen der Formel I, in denen X O, Y OH und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 2Compounds of the formula I in which X is O, Y is OH and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for each compound corresponds to one row of Table A corresponds to Table 2
Verbindungen der Formel I, in denen X O, Y SH und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is O, Y is SH and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for each compound corresponds to one row of Table A.
Tabelle 3 Verbindungen der Formel I, in denen X O, Y NH2 und R1 CH3 bedeuten und die Kombi- nation von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 3 Compounds of the formula I in which X is O, Y is NH 2 and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for each compound corresponds to one row of Table A.
Tabelle 4Table 4
Verbindungen der Formel I, in denen X O, Y NH-CH3 und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 5Compounds of the formula I in which X is O, Y is NH-CH3 and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for each compound corresponds to one row of Table A corresponds to Table 5
Verbindungen der Formel I, in denen X O, Y NH-C2H5 und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 6 Verbindungen der Formel I, in denen X O, Y NH-n-C3H7 und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is O, Y is NH-C2H5 and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for each compound corresponds to one row of Table A. Table 6 Compounds of the formula I in which X is O , Y is NH-n-C3H 7 and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for a compound corresponds in each case to one row of Table A.
Tabelle 7 Verbindungen der Formel I, in denen X O, Y NH-CH(CH3)2 und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 8Table 7 Compounds of the formula I in which X is O, Y is NH-CH (CH 3) 2 and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for each compound corresponds to one row of Table A. Table 8
Verbindungen der Formel I, in denen X O, Y und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 9Compounds of the formula I in which X is O, Y and R 1 are CH 3 and the combination of R 5 and (R 6 ) m for a compound corresponds in each case to one row of Table A corresponds to Table 9
Verbindungen der Formel I, in denen X O, Y NH-CH2CH=CH2 und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is O, Y is NH-CH 2 CH = CH 2 and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for each compound corresponds to one row of Table A.
Tabelle 10 Verbindungen der Formel I, in denen X O, Y NH-CH2C≡CH und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 10 Compounds of the formula I in which X is O, Y is NH-CH 2 C≡CH and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for each compound corresponds to one row of Table A.
Tabelle nTable n
Verbindungen der Formel I, in denen X O, Y NH-CH2CN und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is O, Y is NH-CH 2 CN and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for each compound corresponds to one row of Table A.
Tabelle 12Table 12
Verbindungen der Formel I, in denen X O, Y NH-CH2CeH5 und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is O, Y is NH-CH 2 CeH 5 and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for each compound corresponds to one row of Table A.
Tabelle 13Table 13
Verbindungen der Formel I, in denen X S, Y SH und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is S, Y is SH and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for each compound corresponds to one row of Table A.
Tabelle n Verbindungen der Formel I, in denen X S, Y OH und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable n Compounds of the formula I in which X is S, Y is OH and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for each compound corresponds to one row of Table A.
Tabelle 15Table 15
Verbindungen der Formel I, in denen X S, Y NH2 und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 16Compounds of the formula I in which X is S, Y is NH 2 and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for a compound corresponds in each case to one row of Table A corresponds to Table 16
Verbindungen der Formel I, in denen X S, Y NH-CH3 und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is S, Y is NH-CH 3 and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for each compound corresponds to one row of Table A.
Tabelle 17 Verbindungen der Formel I, in denen X S, Y NH-C2H5 und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 17 Compounds of the formula I in which X is S, Y is NH-C 2 H 5 and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for each compound corresponds to one row of Table A.
Tabelle 18Table 18
Verbindungen der Formel I, in denen X S, Y NH-n-C3H7 und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entspricht Tabelle 19Compounds of the formula I in which X is S, Y is NH-nC 3 H 7 and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for each compound corresponds to one row of Table A. Table 19
Verbindungen der Formel I, in denen X S, Y NH-CH(CH3)2 und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is S, Y is NH-CH (CH 3) 2 and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for each compound corresponds to one row of Table A.
Tabelle 20Table 20
Verbindungen der Formel I, in denen X S, Y und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which XS, Y and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for a compound corresponds in each case to one row of Table A.
Tabelle 21Table 21
Verbindungen der Formel I, in denen X S, Y NH-CH2CH=CH2 und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is S, Y is NH-CH 2 CH = CH 2 and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for each compound corresponds to one row of Table A.
Tabelle 22Table 22
Verbindungen der Formel I, in denen X S, Y NH-CH2C≡CH und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is S, Y is NH-CH 2 C≡CH and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for a compound corresponds in each case to one row of Table A.
Tabelle 23Table 23
Verbindungen der Formel I, in denen X S, Y NH-CH2CN und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is S, Y is NH-CH 2 CN and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for each compound corresponds to one row of Table A.
Tabelle 24Table 24
Verbindungen der Formel I, in denen X S, Y NH-CH2CeH5 und R1 CH3 bedeuten und die Kombination von R5 und (R6)m für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is S, Y is NH-CH 2 CeH 5 and R 1 is CH 3 and the combination of R 5 and (R 6 ) m for each compound corresponds to one row of Table A.
Tabelle A Verbindungen der Formel I, welche der Formel 1.1 A entsprechenTable A Compounds of the formula I which correspond to the formula 1.1A
Die Verbindungen I und deren landwirtschaftlich brauchbaren Salze eignen sich - sowohl als Isomerengemische als auch in Form der reinen Isomeren - als Herbizide. Sie eignen sich als solche oder als entsprechend formuliertes Mittel. Die herbiziden Mittel, die die Verbindung I, insbesondere die bevorzugten Ausgestaltungen davon, enthalten, bekämpfen Pflanzenwuchs auf Nichtkulturflächen sehr gut, besonders bei hohen Aufwandmengen. In Kulturen wie Weizen, Reis, Mais, Soja und Baumwolle wirken sie gegen Unkräuter und Schadgräser, ohne die Kulturpflanzen nennenswert zu schädigen. Dieser Effekt tritt vor allem bei niedrigen Aufwandmengen auf. The compounds I and their agriculturally useful salts are suitable - both as mixtures of isomers and in the form of pure isomers - as herbicides. They are suitable as such or as appropriately formulated agent. The herbicidal compositions containing the compound I, in particular the preferred embodiments thereof, control plant growth on non-crop surfaces very well, especially at high application rates. In crops such as wheat, rice, corn, soybeans and cotton, they act against weeds and grass weeds without significantly damaging the crops. This effect occurs especially at low application rates.
In Abhängigkeit von der jeweiligen Applikationsmethode können die Verbindungen I, insbesondere die bevorzugten Ausgestaltungen davon, bzw. sie enthaltende Mittel noch in einer weiteren Zahl von Kulturpflanzen zur Beseitigung unerwünschter Pflanzen eingesetzt werden. In Betracht kommen beispielsweise folgende Kulturen: Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Avena sati- va, 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 Ii- mon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sa- tivus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgäre, 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 vul- garis, Picea abies, Pinus spec, Pistacia vera, Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Prunus armeniaca, Prunus cerasus, Prunus dulcis und prunus domestica, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Seeale cereale, Sinapis alba, Solanum tuberosum, Sorghum bicolor (s. vulgäre), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticale, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.Depending on the particular application method, the compounds I, in particular the preferred embodiments thereof, or agents containing them can be used in a further number of crop plants for the removal of undesirable plants. For example, the following cultures may be considered: Allium cepa, pineapple comosus, Arachis hypogaea, Asparagus officinalis, Avena sativa, Beta vulgaris spec. altissima, Beta vulgaris spec. rapeseed, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Brassica oleracea, Brassica nigra, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus monon, 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, Seeale cereale, Sinapis alba, Solanum tuberosum, Sorghum bicolor (s. vulgaris), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticale, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.
Der Begriff Kulturpflanzen schließt auch solche ein, die durch Züchtung, Mutagenese oder gentechnische Methoden verändert wurden. Gentechnisch veränderte Pflanzen sind Pflanzen, deren genetisches Material in einer Weise verändert worden ist, wie sie unter natürlichen Bedingungen durch Kreuzen, Mutationen oder natürliche Rekombination (d.h. Neuzusammenstellung der Erbinformation) nicht vorkommt. Dabei werden in der Regel ein oder mehrere Gene in das Erbgut der Pflanze integriert, um die Eigenschaften der Pflanze zu verbessern. Der Begriff Kulturpflanzen umfasst somit auch Pflanzen, die durch züchterische und gentechnische Maßnahmen eine Toleranz gegen bestimmter Herbizidklassen, wieThe term crops also includes those that have been modified by breeding, mutagenesis or genetic engineering methods. Genetically engineered plants are plants whose genetic material has been altered in a way that does not occur under natural conditions by crossing, mutations or natural recombination (i.e., rearrangement of genetic information). As a rule, one or more genes are integrated into the genome of the plant in order to improve the properties of the plant. The term crops thus also encompasses plants which, by breeding and genetic engineering measures, tolerate certain herbicide classes, such as
Hydroxyphenylpyruvat-Dioxygenase (HPPD)-Inhibitoren, Acetolactat-Synthase (ALS)- Inhibitoren, wie z. B. Sulfonylharnstoffe (EP-A 257 993, US 5,013,659) oder Imidazoli- none (siehe z. B. 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), Enolpyruvylshikimat-3-Phosphat- Synthase (EPSPS)-lnhibitoren wie z. B. Glyphosat (siehe z. B. WO 92/00377), Gluta- minsynthetase (GS)-lnhibitoren wie z. B. Glufosinat (siehe z. B. EP-A 242 236, EP-A 242 246) oder Oxynil-Herbizide (siehe z. B. US 5,559,024) erworben haben.Hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, acetolactate synthase (ALS) inhibitors, such as. As sulfonylureas (EP-A 257 993, US 5,013,659) or imidazolium none (see eg 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. Glyphosate (see, for example, WO 92/00377), glutamine synthetase (GS) inhibitors such as. Glufosinate (see eg EP-A 242 236, EP-A 242 246) or oxynil herbicides (see eg US 5,559,024).
Mit Hilfe klassischer Züchtungsmethoden (Mutagenese) wurden zahlreiche Kulturpflanzen, z. B. Clearfield®-Raps, erzeugt, die eine Toleranz gegen Imidazolinone, z. B. Imazamox, haben. Mit Hilfe gentechnischer Methoden wurden Kulturpflanzen, wie So- ja, Baumwolle, Mais, Rüben und Raps, erzeugt, die resistent gegen Glyphosat oder Glufosinat sind, erzeugt, welche unter den Handelsnamen RoudupReady® (Glyphosat) und Liberty Link® (Glufosinat) erhältlich sind.With the help of classical breeding methods (mutagenesis) numerous crops, eg. As Clearfield® rapeseed, which produces a tolerance to imidazolinones, z. As imazamox, have. With Crop plants were as solar yes, produces cotton, corn, beet and oilseed rape, against glyphosate or glufosinate resistant, produced under the trade name RoudupReady ® (glyphosate) and Liberty Link ® (glufosinate) have ,
Der Begriff Kulturpflanzen umfasst somit auch Pflanzen, die mit Hilfe gentechnischer Maßnahmen ein oder mehrere Toxine, z. B. solche aus dem Bakterienstamm Bacillus ssp., produzieren. Toxine, die durch solche gentechnisch veränderten Pflanzen hergestellt werden, umfassen z. B. insektizide Proteine von Bacillus spp., insbesondere von B. thuringiensis, wie die Endotoxine CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 , Cry9c, Cry34Ab1 oder Cry35Ab1 ; oder vegetative insektizide Proteine (VIPs), z. B. VIP1 , VIP2, VIP3, oder VIP3A; insektizide Proteine von Nematoden- kolonisierenden Bakterien, z. B. Photorhabdus spp. oder Xenorhabdus spp.; Toxine aus tierischen Organismen, z. B. Wepsen,-, Spinnen- oder Skorpionstoxine; pilzliche Toxine, z. B. aus Streptomyceten; pflanzliche Lektine, z. B. aus Erbse oder Gerste; Agglutinine; Proteinase-Inhibitoren, z. B. Trypsin-Inhibitoren, Serinprotease-Inhibitoren, Patatin, Cystatin oder Papain-Inhibitoren; Ribosomen-inaktivierende Proteine (RIPs), z. B. Ricin, Mais-RIP, Abrin, Luffin, Saporin oder Bryodin; Steroid-metabolisierendeThe term crops thus also includes plants that use genetic engineering measures one or more toxins, eg. As those from the bacterial strain Bacillus ssp., Produce. Toxins produced by such genetically engineered plants include e.g. Insecticidal proteins of Bacillus spp., In particular B. thuringiensis such as the endotoxins CrylAb, CrylAc, CrylF, Cry1Fe2, Cry2Ab, Cry3A, Cry3Bb1, Cry9c, Cry34Ab1 or Cry35Ab1; or vegetative insecticidal proteins (VIPs), e.g. VIP1, VIP2, VIP3, or VIP3A; insecticidal proteins of nematode-colonizing bacteria, e.g. B. Photorhabdus spp. or Xenorhabdus spp .; Toxins from animal organisms, eg. B. Wepsen, spider or scorpion toxins; fungal toxins, e.g. B. from streptomycetes; herbal lectins, e.g. From pea or barley; agglutinins; Proteinase inhibitors, e.g. Trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; Ribosome Inactivating Proteins (RIPs), e.g. Ricin, corn RIP, abrin, luffin, saporin or bryodin; Steroid metabolizing
Enzyme, z. B. 3-Hydroxysteroid-Oxidase, Ecdysteroid-IDP-Glycosyl-Transferase, Cho- lesterinoxidase, Ecdyson-Inhibitoren oder HMG-CoA-Reduktase; lonenkanalblocker, z. B. Inhibitoren von Natrium- oder Calziumkanälen; Juvenilhormon-Esterase; Rezeptoren für das diuretischen Hormon (Helicokininrezeptoren); Stilbensynthase, Bibenzyl- synthase, Chitinasen und Glucanasen. Diese Toxine können in den Pflanzen auch als Prätoxine, Hybridproteine, verkürzte oder anderweitig modfizierte Proteine produziert werden. Hybridproteine zeichnen sich durch eine neue Kombination von verschiedenen Proteindomänen aus (siehe z. B. WO 2002/015701). Weitere Besipiele für derartige Toxine oder gentechnisch veränderte Pflanzen, die diese Toxine produzieren sind in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878,Enzymes, e.g. 3-hydroxysteroid oxidase, ecdysteroid IDP glycosyltransferase, cholesterol oxidase, ecdysone inhibitors or HMG-CoA reductase; ion channel blocker, e.g. B. inhibitors of sodium or calcium channels; Juvenile hormone esterase; Receptors for the diuretic hormone (helicokinin receptors); Stilbene synthase, bibenzyl synthase, chitinases and glucanases. These toxins can also be produced in the plants as proteoxins, hybrid proteins, 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 described in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878,
WO 03/018810 und WO 03/052073 offenbart. Die Methoden zur Herstellung dieser gentechnisch veränderten Pflanzen sind dem Fachmann bekannt und z. B. in den oben erwähnten Publikationen dargelegt. Zahlreiche der zuvor genannten Toxine verleihen den Pflanzen, die diese produzieren, eine Toleranz gegen Schädlinge aus allen taxo- nomischen Arthropodenklassen, insbesondere gegen Käfer (Coeleropta), Zweiflügler (Diptera) und Schmetterlinge (Lepidoptera) und gegen Nematoden (Nematoda). Gentechnisch veränderte Pflanzen, die ein oder mehrere Gene, die für insektizide Toxine kodieren, produzieren sind z. B. in den oben erwähnten Publikationen beschrieben und zum Teil kommerziell erhältlich, wie z. B. YieldGard® (Maissorten, die das Toxin CrylAb produzieren), YieldGard® Plus (Maissorten, die die Toxine CrylAb und Cry3Bb1 produzieren), Starlink® (Maissorten, die das Toxin Cry9c produzieren), Herculex® RW (Maissorten, die die Toxine Cry34Ab1 , Cry35Ab1 und das Enzym Phosphinothricin-N-Acetyltransferase [PAT] produzieren); NuCOTN® 33B (Baumwollsorten, die das Toxin CrylAc produzieren), Bollgard® I (Baumwollsorten, die das Toxin CrylAc produzieren), Bollgard® Il (Baumwollsorten, die die Toxine CrylAc und Cry2Ab2 produzieren); VIPCOT® (Baumwollsorten, die ein VIP-Toxin produzieren); NewLeaf® (Kartoffelsorten, die das Toxin Cry3A produzieren); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt11 (z. B. Agrisure® CB) und Bt176 von Syngenta Seeds SAS, Frankreich, (Maissorten, die das Toxin CrylAb und das PAT-Enyzm produzieren), MIR604 von Syngenta Seeds SAS, Frankreich (Maissorten, die ein modifi- zierte Version des Toxins Cry3A produzieren, siehe hierzu WO 03/018810), MON 863 von Monsanto Europe S.A., Belgien (Maissorten, die das Toxin Cry3Bb1 produzieren), IPC 531 von Monsanto Europe S.A., Belgien (Baumwollsorten, die eine modifizierte Version des Toxins CrylAc produzieren) und 1507 von Pioneer Overseas Corporation, Belgien (Maissorten, die das Toxin Cryl F und das PAT-Enyzm produzieren). Der Begriff Kulturpflanzen umfasst somit auch Pflanzen, die mit Hilfe gentechnischer Maßnahmen ein oder mehrere Proteine produzieren, die eine erhöhte Resistenz oder Widerstandfähigkeit gegen bakterielle, virale oder pilzliche Pathogene bewirken, wie z. B. sogenannte Pathogenesis-related-Proteine (PR-Proteine, siehe EP-A 392 225), Resistenzproteine (z. B. Kartoffelsorten, die zwei Resistenzgene gegen Phytophthora infestans aus der mexikanischen Wildkartoffel Solanum bulbocastanum produzieren) oder T4-Lysozym (z. B. Kartoffelsorten, die durch die Produktion diese Proteins resistent gegen Bakterien wie Erwinia amylvora ist).WO 03/018810 and WO 03/052073. The methods for producing these genetically modified plants are known in the art and z. As set forth in the publications mentioned above. Many of the aforementioned toxins confer on the plants that produce them a tolerance to pests of all taxonomic arthropod classes, in particular to beetles (Coeleropta), diptera (Diptera) and butterflies (Lepidoptera) and nematodes (Nematoda). Genetically engineered plants that produce one or more genes encoding insecticidal toxins, e.g. As described in the publications mentioned above and partly commercially available, such as. B. YieldGard ® (corn cultivars producing the toxin CrylAb), YieldGard ® Plus (corn cultivars producing the toxins CrylAb and Cry3Bb1), StarLink ® (corn cultivars producing the toxin Cry9c), Herculex ® RW (corn cultivars toxins which Cry34Ab1, Cry35Ab1 and the enzyme phosphinothricin N-acetyltransferase [PAT] produce); NuCOTN ® 33B (cotton cultivars producing the toxin CrylAc), Bollgard ® I (cotton cultivars producing the toxin CrylAc), Bollgard ® Il (cotton cultivars producing the toxins CrylAc and Cry2Ab2); VIPCOT ® (cotton varieties that produce a VIP toxin); NewLeaf ® (potato cultivars producing the Cry3A toxin); Bt Xtra ®, NatureGard® ®, KnockOut ®, BiteGard ®, Protecta ®, Bt11 (z. B. Agrisure ® CB) and Bt176 from Syngenta Seeds SAS, France (corn varieties which produce the toxin CrylAb and the PAT enzyme) , MIR604 from Syngenta Seeds SAS, France (maize strains producing a modified version of the toxin Cry3A, see WO 03/018810), MON 863 from Monsanto Europe SA, Belgium (maize strains producing the toxin Cry3Bb1), IPC 531 from Monsanto Europe SA, Belgium (cottons producing a modified version of the toxin CrylAc) and 1507 from Pioneer Overseas Corporation, Belgium (maize varieties producing the toxin Cryl F and the PAT enzyme). The term crops thus also includes plants that produce by genetic engineering measures one or more proteins that cause increased resistance or resistance to bacterial, viral or fungal pathogens, such as. B. so-called pathogenesis-related proteins (PR proteins, see EP-A 392 225), resistance proteins (eg, potato varieties that produce two resistance genes against Phytophthora infestans from the Mexican wild potato Solanum bulbocastanum) or T4 lysozyme (z. Potato varieties resistant to bacteria such as Erwinia amylvora by the production of this protein).
Der Begriff Kulturpflanzen umfasst somit auch Pflanzen, deren Produktivität mit Hilfe gentechnischer Methoden verbessert wurde, indem z. B. die Ertragsfähigkeit (z. B. Biomasse, Kornertrag, Stärke-, Öl- oder Proteingehalt), die Toleranz gegenüber Trockenheit, Salz oder anderen begrenzenden Umweltfaktoren oder die Widerstandsfähigkeit gegenüber Schädlingen und pilzlichen, bakteriellen und viralen Pathogenen gesteigert wird. Der Begriff Kulturpflanzen umfasst auch Pflanzen, deren Inhaltsstoffe insbesondere zur Verbesserung der menschlichen oder tierischen Ernährung mit Hilfe gentechnischer Methoden verändert wurden, indem z. B. Ölpflanzen gesundheitsfördernde lang- kettige Omega-3-Fettsäuren oder einfach ungesättigte Omega-9-Fettsäuren (z. B. Ne- xera®-Raps) produzieren. Der Begriff Kulturpflanzen umfasst auch Pflanzen, die zur verbesserten Produktion von Rohstoffen mit Hilfe gentechnischer Methoden verändert wurden, indem z. B. der Amylopektin-Gehalt von Kartoffeln (Amflora®-Kartoffel) erhöht wurde. Des Weiteren wurde gefunden, dass die Verbindungen der Formel I auch zur Defoli- ation und/oder Desikkation von Pflanzenteilen geeignet ist, wofür Kulturpflanzen wie Baumwolle, Kartoffel, Raps, Sonnenblume, Sojabohne oder Ackerbohnen, insbesondere Baumwolle, in Betracht kommen. Diesbezüglich wurden Mittel zur Desikkation und /oder Defoliation von Pflanzen, Verfahren zur Herstellung dieser Mittel und Verfahren zur Desikkation und/oder Defoliation von Pflanzen mit der Verbindungen der Formel I gefunden.The term crops thus also includes plants whose productivity has been improved by means of genetic engineering methods by z. For example, yield (eg 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 may be increased. The term crops also includes plants whose ingredients have been modified in particular to improve the human or animal diet using genetic engineering methods by z. For example, oil plants can produce health-promoting long-chain omega-3 fatty acids or monounsaturated omega-9 fatty acids (eg Nexera ® oilseed rape). The term crops also includes plants that have been modified for the improved production of raw materials by means of genetic engineering methods by z. B. the amylopectin content of potatoes (Amflora ® potato) was increased. 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, come into consideration. In this regard, compositions for the desiccation and / or defoliation of plants, processes for the preparation of these agents and methods for the desiccation and / or defoliation of plants with the compounds of formula I have been found.
Als Desikkantien eignen sich die Verbindungen der Formel I insbesondere zur Austrocknung der oberirdischen Teile von Kulturpflanzen wie Kartoffel, Raps, Sonnenblu- me und Sojabohne aber auch Getreide. Damit wird ein vollständig mechanisches Be- ernten dieser wichtigen Kulturpflanzen ermöglicht.As desiccants, the compounds of formula I are particularly suitable for dehydration of the aerial parts of crop plants such as potato, oilseed rape, sunflower and soybean but also cereals. This enables a completely mechanical harvesting of these important crops.
Von wirtschaftlichem Interesse ist ferner die Ernteerleichterung, die durch das zeitlich konzentrierte Abfallen oder Vermindern der Haftfestigkeit am Baum bei Zitrusfrüch- ten, Oliven oder bei anderen Arten und Sorten von Kern-, Stein- und Schalenobst ermöglicht wird. Derselbe Mechanismus, d.h., die Förderung der Ausbildung von Trenngewebe zwischen Frucht- oder Blatt- und Sprossteil der Pflanzen ist auch für ein gut kontrollierbares Entblättern von Nutzpflanzen, insbesondere Baumwolle, wesentlich. Außerdem führt die Verkürzung des Zeitintervalls, in dem die einzelnen Baumwoll- pflanzen reif werden, zu einer erhöhten Qualität der Faser nach der Ernte.Also of economic interest is harvest facilitation, which is made possible by the time-concentrated dropping or reducing the adhesion of the tree to citrus fruit, olives or other types and varieties of pome, stone and peel fruit. The same mechanism, i.e. promoting the formation of release webs between fruit or leaf and shoot part of the plants, is also essential for a well controllable defoliation of crops, especially cotton. In addition, shortening the time interval in which each cotton plant ripens leads to increased fiber quality after harvest.
Die Verbindungen I bzw. die sie enthaltenden herbiziden Mittel können beispielsweise in Form von direkt versprühbaren wäßrigen Lösungen, Pulvern, Suspensionen, auch hochprozentigen wäßrigen, öligen oder sonstigen Suspensionen oder Dispersio- nen, Emulsionen, Öldispersionen, Pasten, Stäubemitteln, Streumitteln oder Granulaten durch Versprühen, Vernebeln, Verstäuben, Verstreuen, Gießen oder Behandlung des Saatgutes bzw. Mischen mit dem Saatgut angewendet werden. Die Anwendungsformen richten sich nach den Verwendungszwecken; sie sollten in jedem Fall möglichst die feinste Verteilung der erfindungsgemäßen Wirkstoffe gewährleisten. Die herbiziden Mittel enthalten eine herbizid wirksame Menge mindestens einer Verbindung der Formel I oder eines landwirtschaftlich brauchbaren Salzes von I und für die Formulierung von Pflanzenschutzmitteln übliche Hilfsstoffe.The compounds I or the herbicidal compositions containing them, for example in the form of directly sprayable aqueous solutions, powders, suspensions, even high-percentage aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents or granules by spraying , Misting, dusting, scattering, pouring or treatment of the seed or mixing with the seed. The forms of application depend on the intended use; In any case, they should ensure the finest possible distribution of the active compounds according to the invention. The herbicidal compositions contain a herbicidally effective amount of at least one compound of the formula I or an agriculturally useful salt of I and auxiliaries customary for the formulation of pesticides.
Beispiele für die Formulierung von Pflanzenschutzmitteln übliche Hilfsmittel sind i- nerte Hilfsstoffe, feste Trägerstoffe, oberflächenaktive Stoffe (wie Dispergiermittel Schutzkolloide, Emulgatoren, Netzmittel und Haftmittel), organische und anorganische Verdicker, Bakterizide, Frostschutzmittel, Entschäumer ggf. Farbstoffe und für Saatgutformulierungen Kleber.Examples of the Formulation of Pesticides Commonly used auxiliaries are preferred auxiliaries, solid carriers, surface-active substances (such as dispersants, protective colloids, emulsifiers, wetting agents and adhesives), organic and inorganic thickeners, bactericides, antifreeze agents, defoamers, if necessary, dyes and for seed formulations adhesives.
Beispiele für Verdicker (d.h. Verbindungen, die der Formulierung ein modifiziertes Fließverhalten verleihen, d.h. hohe Viskosität im Ruhezustand und niedrige Viskosität im bewegten Zustand) sind Polysaccharide wie Xanthan Gum (Kelzan® der Fa. Kelco), Rhodopol® 23 (Rhone Poulenc) oder Veegum® (Firma RT. Vanderbilt) sowie organische und anorganische Schichtmineralienwie Attaclay® (Firma Engelhardt). Beispiele für Antischaummittel sind Silikonemulsionen (wie z.Bsp. Silikon® SRE, Firma Wacker oder Rhodorsil® der Firma Rhodia ), langkettige Alkohole, Fettsäuren, Salze von Fettsäuren, fluororganische Verbindungen und deren Gemische.Examples of thickeners (ie, compounds which impart modified flowability to the formulation, ie, high-level at low viscosity and low viscosity in the agitated state) are polysaccharides such as xanthan gum (Kelzan® from Kelco), Rhodopol® 23 (Rhone Poulenc) or Veegum ® (RT Vanderbilt) and organic and inorganic layer minerals such as Attaclay® (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.
Bakterizide können zur Stabilisierung der wäßrigen Herbizid-Formulierung zugesetzt werden. Beispiele für Bakterizide sind Bakterizide basierend auf Diclorophen und Ben- zylalkoholhemiformal (Proxel® der Fa. ICI oder Acticide® RS der Fa. Thor Chemie und Kathon® MK der Firma Rohm & Haas) sowie Isothiazolinonderivaten wie Alkylisothia- zolinonen und Benzisothiazolinonen (Acticide MBS der Fa. Thor Chemie)Bactericides may be added to stabilize the aqueous herbicidal formulation. Examples of bactericides are bactericides based on diclorophene and benzyl alcohol hemiformal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas) and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acticide MBS der Fa. Thor Chemie)
Beispiele für Frostschutzmittel sind Ethylenglycol, Propylenglycol, Harnstoff oder Glycerin.Examples of antifreeze agents are ethylene glycol, propylene glycol, urea or glycerol.
Beispiele für Farbmittel sind sowohl in Wasser wenig lösliche Pigmente als auch in Wasser lösliche Farbstoffe. Als Beispiele genannt seien die unter den Bezeichnungen Rhodamin B, Cl. Pigment Red 112 und Cl. Solvent Red 1 bekannten Farbstoffe, sowie pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pig- ment 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. Beispiele für Kleber sind Polyvinylpyrrolidon, Polyvinylacetat, Polyvinylalkohol und Tylose.Examples of colorants are both water-insoluble pigments and water-soluble dyes. Examples which may be mentioned under the names rhodamine B, Cl. Pigment Red 112 and Cl. Solvent Red 1 known dyes, and 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: 1, 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 polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose.
Als inerte Zusatzstoffe kommen beispielsweise in Betracht:Suitable inert additives are, for example:
Mineralölfraktionen von mittlerem bis hohem Siedepunkt, wie Kerosin oder Dieselöl, ferner Kohlenteeröle sowie Öle pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, z.B. Paraffin, Tetrahydronaphthalin, alkylierte Naphthaline oder deren Derivate, alkylierte Benzole oder deren Derivate, Alkohole wie Methanol, Ethanol, Propanol, Butanol, Cyclohexanol, Ketone wie Cycloh- exanon oder stark polare Lösungsmittel, z. B. Amine wie N-Methylpyrrolidon oder Wasser.Mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, eg. As amines such as N-methylpyrrolidone or water.
Feste Trägerstoffe sind Mineralerden wie Kieselsäuren, Kieselgele, Silikate, Talkum, Kaolin, Kalkstein, Kalk, Kreide, Bolus, Löß, Ton, Dolomit, Diatomeenerde, Calcium- und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Düngemittel, wie Ammoniumsulfat, Ammoniumphosphat, Ammoniumnitrat, Harnstoffe und pflanzliche Pro- dukte wie Getreidemehl, Baumrinden-, Holz- und Nußschalenmehl, Cellulosepulver oder andere feste Trägerstoffe.Solid carriers are mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
Als oberflächenaktive Stoffe (Adjuvantien, Netz-, Haft-, Dispergier- sowie Emulgiermittel) kommen die Alkali-, Erdalkali-, Ammoniumsalze von aromatischen Sulfonsäu- ren, z.B. Ligninsulfonsäuren (z.B. Borrespers-Typen, Borregaard), Phenolsulfonsäuren, Naphthalinsulfonsäuren (Morwet-Typen, Akzo Nobel) und Dibutylnaphthalinsulfonsäure (Nekal-Typen, BASF SE), sowie von Fettsäuren, Alkyl- und Alkylarylsulfonaten, Alkyl-, Laurylether- und Fettalkoholsulfaten, sowie Salze sulfatierter Hexa-, Hepta- und Octa- decanolen sowie von Fettalkoholglykolether, Kondensationsprodukte von sulfoniertem Naphthalin und seiner Derivate mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphthalinsulfonsäuren mit Phenol und Formaldehyd, Polyoxyethylen- octylphenolether, ethoxyliertes Isooctyl-, Octyl- oder Nonylphenol, Alkylphenyl-, Tribu- tylphenylpolyglykolether, Alkylarylpolyetheralkohole, Isotridecylalkohol, Fettalkoholethy- lenoxid-Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylenalkylether oder Polyoxy- propylenalkylether, Laurylalkoholpolyglykoletheracetat, Sorbitester, Lignin-Sulfitablau- gen sowie Proteine, denaturierte Proteine, Polysaccharide (z.B. Methylcellulose), hydrophob modifizierte Stärken, Polyvinylalkohol (Mowiol typen Clariant), Polycarboxylate (BASF SE, Sokalan-Typen), Polyalkoxylate, Polyvinylamin (BASF SE, Lupamin- Typen), Polyethylenimin (BASF SE, Lupasol-Typen) , Polyvinylpyrrolidon und deren Copolymere in Betracht.As surface-active substances (adjuvants, wetting agents, adhesives, dispersants and emulsifiers), the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, eg lignosulfonic acids (eg Borrespers types, Borregaard), phenolsulfonic acids, naphthalenesulfonic acids (Morwet types , Akzo Nobel) and dibutylnaphthalenesulfonic acid (Nekal types, BASF SE), as well as fatty acids, alkyl and alkylaryl sulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octa- decanols and also of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tributylphenyl polyglycol ethers, alkylarylpolyether alcohols, isotridecylalcohol , Fatty alcohol-ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin sulfite deposits and proteins, denatured proteins, polysaccharides (eg 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.
Pulver-, Streu- und Stäubemittel können durch Mischen oder gemeinsames Vermählen der wirksamen Substanzen mit einem festen Trägerstoff hergestellt werden. Granulate, z.B. Umhüllungs-, Imprägnierungs- und Homogengranulate können durch Bindung der Wirkstoffe an feste Trägerstoffe hergestellt werden.Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier. Granules, e.g. Coating, impregnation and homogeneous granules can be prepared by binding the active compounds to solid carriers.
Wässrige Anwendungsformen können aus Emulsionskonzentraten, Suspensionen, Pasten, netzbaren Pulvern oder wasserdispergierbaren Granulaten durch Zusatz von Wasser bereitet werden. Zur Herstellung von Emulsionen, Pasten oder Öldispersionen können die Verbindungen der Formel I oder Ia als solche oder in einem Öl oder Lösungsmittel gelöst, mittels Netz-, Haft-, Dispergier- oder Emulgiermittel in Wasser homogenisiert werden. Es können aber auch aus wirksamer Substanz, Netz-, Haft-, Dispergier- oder Emulgiermittel und eventuell Lösungsmittel oder Öl bestehende Konzentrate hergestellt werden, die zur Verdünnung mit Wasser geeignet sind. Die Konzentrationen der Verbindungen der Formel I in den anwendungsfertigen Zubereitungen können in weiten Bereichen variiert werden. Die Formulierungen enthalten im Allgemeinen 0,001 bis 98 Gew.-%, vorzugsweise 0,01 bis 95 Gew.-%, mindestens eines Wirkstoffs. Die Wirkstoffe werden dabei in einer Reinheit von 90% bis 100%, vorzugsweise 95% bis 100% (nach NMR-Spektrum) eingesetzt.Aqueous application 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 Ia, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agents, tackifiers, dispersants or emulsifiers. However, it is also possible to prepare concentrates consisting of active substance, wetting, adhesion, dispersing or emulsifying agent and possibly solvent or oil, which are suitable for dilution with water. The concentrations of the compounds of the formula I in the ready-to-use formulations can be varied within wide limits. The formulations generally contain from 0.001 to 98% by weight, preferably from 0.01 to 95% by weight, of at least one active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
Die erfindungsgemäßen Verbindungen I können beispielsweise wie folgt formuliert werden:The compounds I according to the invention can be formulated, for example, as follows:
1. Produkte zur Verdünnung in Wasser A Wasserlösliche Konzentrate 10 Gew.-Teile Wirkstoff werden mit 90 Gew.-Teilen Wasser oder einem wasserlöslichen Lösungsmittel gelöst. Alternativ werden Netzmittel oder andere Hilfsmittel zugefügt. Bei der Verdünnung in Wasser löst sich der Wirkstoff. Man erhält auf diese Weise eine Formulierung mit 10 Gew.-% Wirkstoffgehalt. B Dispergierbare Konzentrate 20 Gew.-Teile Wirkstoff werden in 70 Gew.-Teilen Cyclohexanon unter Zusatz von 10 Gew.-Teilen eines Dispergiermittels z.B. Polyvinylpyrrolidon gelöst. Bei Verdünnung in Wasser ergibt sich eine Dispersion. Der Wirkstoffgehalt beträgt 20 Gew.-% C Emulgierbare Konzentrate1. Products for dilution in water A Water-soluble concentrates 10 parts by weight of active compound are dissolved with 90 parts by weight of water or a water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the active ingredient dissolves. This gives a formulation with 10 wt .-% active ingredient content. 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 in water gives a dispersion. The active ingredient content is 20% by weight C Emulsifiable concentrates
15 Gew.-Teile Wirkstoff werden in 75 Gew.-Teilen eines organisches Lösungsmittels (z.B. Alkylaromaten)-unter Zusatz von Ca-Dodecylbenzolsulfonat und Ricinusölethoxy- lat (jeweils 5 Gew.-Teile) gelöst. Bei der Verdünnung in Wasser ergibt sich eine Emul- sion. Die Formulierung hat 15 Gew.-% Wirkstoffgehalt.15 parts by weight of active compound are dissolved in 75 parts by weight of an organic solvent (for example alkylaromatics) with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution in water results in an emulsion. The formulation has 15% by weight active ingredient content.
D EmulsionenD emulsions
25 Gew.-Teile Wirkstoff werden in 35 Gew.-Teilen eines organisches Lösungsmittels (z.B. Alkylaromaten) unter Zusatz von Ca-Dodecylbenzolsulfonat und Ricinusölethoxy- lat (jeweils 5 Gew.-Teile) gelöst. Diese Mischung wird mittels einer Emulgiermaschine (z.B. Ultraturax) in 30 Gew.Teile Wasser gegeben und zu einer homogenen Emulsion gebracht. Bei der Verdünnung in Wasser ergibt sich eine Emulsion. Die Formulierung hat einen Wirkstoffgehalt von 25 Gew.-%.25 parts by weight of active compound are dissolved in 35 parts by weight of an organic solvent (for example alkylaromatics) with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is added to water by means of an emulsifying machine (e.g., Ultraturax) in 30 parts by weight and made into a homogeneous emulsion. Dilution in water results in an emulsion. The formulation has an active ingredient content of 25% by weight.
E Suspensionen 20 Gew.-Teile Wirkstoff werden unter Zusatz von 10 Gew.-Teilen Dispergier- und Netzmitteln und 70 Gew.-Teilen Wasser oder einem organischen Lösungsmittel in einer Rührwerkskugelmühle zu einer feinen Wirkstoffsuspension zerkleinert. Bei der Verdünnung in Wasser ergibt sich eine stabile Suspension des Wirkstoffs. Der Wirkstoffgehalt in der Formulierung beträgt 20 Gew.-% . F Wasserdispergierbare und wasserlösliche Granulate 50 Gew.-Teile Wirkstoff werden unter Zusatz von 50 Gew-Teilen Dispergier- und Netzmitteln fein gemahlen und mittels technischer Geräte (z.B. Extrusion, Sprühturm, Wirbelschicht) als wasserdispergierbare oder wasserlösliche Granulate hergestellt. Bei der Verdünnung in Wasser ergibt sich eine stabile Dispersion oder Lösung des Wirkstoffs. Die Formulierung hat einen Wirkstoffgehalt von 50 Gew.-%. G Wasserdispergierbare und wasserlösliche PulverE Suspensions 20 parts by weight of active compound are comminuted with the addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent in a stirred ball mill to give a fine active substance suspension. Dilution in water results in a stable suspension of the active ingredient. The active ingredient content in the formulation is 20% by weight. F Water-dispersible and water-soluble granules 50 parts by weight of active compound are finely ground with the addition of 50 parts by weight of dispersing and wetting agents and prepared by means of industrial equipment (for example extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient. The formulation has an active ingredient content of 50% by weight. G Water-dispersible and water-soluble powders
75 Gew.-Teile Wirkstoff werden unter Zusatz von 25 Gew.-Teilen Dispergier- und Netzmitteln sowie Kieselsäuregel in einer Rotor-Strator Mühle vermählen. Bei der Verdünnung in Wasser ergibt sich eine stabile Dispersion oder Lösung des Wirkstoffs. Der Wirkstoffgehalt der Formulierung beträgt 75 Gew.-%. H Gelformulierungen75 parts by weight of active compound are ground with the addition of 25 parts by weight of dispersing and wetting agents and silica gel in a rotor-Strator mill. Dilution in water results in a stable dispersion or solution of the active ingredient. The active ingredient content of the formulation is 75% by weight. H gel formulations
In einer Kugelmühle werden 20 Gew.-Teile Wirkstoff, 10 Gew.-Teile Dispergiermittel, 1 Gew.-Teil Geliermittel und 70 Gew.-Teile Wasser oder eines organischen Lösungsmittels zu einer feinen Suspension vermählen. Bei der Verdünnung mit Wasser ergibt sich eine stabile Suspension mit 20 Gew.-% Wirkstoffgehalt.In a ball mill, 20 parts by weight of the active ingredient, 10 parts by weight of the dispersant, 1 part by weight of the gelling agent and 70 parts by weight of water or an organic solvent are ground to a fine suspension. Dilution with water results in a stable suspension with 20% by weight active ingredient content.
2. Produkte für die Direktapplikation I Stäube2. Products for direct application I dusts
5 Gew.-Teile Wirkstoff werden fein gemahlen und mit 95 Gew.-Teilen feinteiligem Kaolin innig vermischt. Man erhält dadurch ein Stäubemittel mit 5 Gew.-% Wirkstoffgehalt. J Granulate (GR, FG, GG, MG)5 parts by weight of active compound are finely ground and intimately mixed with 95 parts by weight of finely divided kaolin. This gives a dust with 5 wt .-% active ingredient content. J Granules (GR, FG, GG, MG)
0,5 Gew-Teile Wirkstoff werden fein gemahlen und mit 99,5 Gewichtsteilen Trägerstoffe verbunden. Gängige Verfahren sind dabei die Extrusion, die Sprühtrocknung oder die Wirbelschicht. Man erhält dadurch ein Granulat für die Direktapplikation mit 0,5 Gew.-% Wirkstoffgehalt.0.5 parts by weight of active compound are finely ground and combined with 99.5 parts by weight of carriers. Common processes are extrusion, spray drying or the fluidized bed. This gives a granulate for direct application with 0.5 wt .-% active ingredient content.
K ULV- Lösungen (UL)K ULV solutions (UL)
10 Gew.-Teile Wirkstoff werden in 90 Gew.-Teilen eines organischen Lösungsmittels z.B. XyIoI gelöst. Dadurch erhält man ein Produkt für die Direktapplikation mit 10 Gew.- % Wirkstoffgehalt.10 parts by weight of active compound are dissolved in 90 parts by weight of an organic solvent, e.g. XyIoI solved. This gives a product for direct application with 10% by weight of active ingredient content.
Die Applikation der Verbindungen I oder der sie enthaltenden herbiziden Mittel kann im Vorauflauf-, im Nachauflaufverfahren oder zusammen mit dem Saatgut einer Kultur- pflanze erfolgen. Es besteht auch die Möglichkeit, die herbiziden Mittel bzw. Wirkstoffe dadurch zu applizieren, dass mit den herbiziden Mitteln bzw. Wirkstoffen vorbehandeltes Saatgut einer Kulturpflanze ausgebracht wird. Sind die Wirkstoffe für gewisse Kulturpflanzen weniger verträglich, so können Ausbringungstechniken angewandt werden, bei welchen die herbiziden Mittel mit Hilfe der Spritzgeräte so gespritzt werden, daß die Blätter der empfindlichen Kulturpflanzen nach Möglichkeit nicht getroffen werden, während die Wirkstoffe auf die Blätter darunter wachsender unerwünschter Pflanzen oder die unbedeckte Bodenfläche gelangen (post-directed, lay-by).The application of the compounds I or the herbicidal compositions containing them can take place in the pre-emergence, post-emergence or together with the seed of a crop. It is also possible to apply the herbicidal compositions or active ingredients characterized in that with the herbicidal agents or active ingredients pretreated seed of a crop plant is applied. If the active ingredients are less compatible with certain crops, then application techniques may be employed whereby the herbicidal agents are sprayed by the sprayers so as not to hit the leaves of the sensitive crops as far as possible, while the active ingredients affect the leaves underneath growing undesirable plants or the uncovered floor surface (post-directed, lay-by).
In einer weiteren Ausführungsform kann die Applikation der Verbindungen der For- mel I bzw. der herbiziden Mittel durch Behandlung von Saatgut erfolgen.In a further embodiment, the application of the compounds of the formula I or of the herbicidal compositions can be carried out by treating seed.
Die Behandlung von Saatgut umfasst im Wesentlichen alle dem Fachmann geläufigen Techniken (seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping, und seed pelleting) basierend auf den erfindungsgemäßen Verbindungen der Formel I bzw. daraus herge- stellten Mitteln. Hierbei können die herbiziden Mittel verdünnt oder unverdünnt aufgetragen werden.The treatment of seed comprises essentially all techniques familiar to the skilled worker (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 according to the invention I or funds produced therefrom. Here, the herbicidal agents can be diluted or applied undiluted.
Der Begriff Saatgut umfasst Saatgut aller Arten, wie z.B. Körner, Samen, Früchte, Knollen, Stecklinge und ähnliche Formen. Bevorzugt beschreibt der Begriff Saatgut hier Körner und Samen. Als Saatgut kann Saatgut der oben erwähnten Nutzpflanzen aber auch das Saatgut transgener oder durch herkömmliche Züchtungsmethoden erhaltener Pflanzen eingesetzt werden.The term seed includes seeds of all kinds, e.g. Grains, seeds, fruits, tubers, cuttings and similar forms. The term seed preferably describes grains and seeds here. Seeds of the abovementioned crops but also the seeds of transgenic or obtained by conventional breeding methods plants can be used as seeds.
Die Aufwandmengen an Wirkstoff betragen je nach Bekämpfungsziel, Jahreszeit, Zielpflanzen und Wachstumsstadium 0.001 bis 3.0, vorzugsweise 0.01 bis 1.0 kg/ha aktive Substanz (a. S.). Zur Saatgutbehandlung werden die Verbindungen I üblicherweise in Mengen von 0,001 bis 10 kg pro 100 kg Saatgut eingesetzt.Depending on the control target, season, target plants and growth stage, the application rates of active ingredient are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (a. S.). For seed treatment, the compounds I are usually used in amounts of 0.001 to 10 kg per 100 kg of seed.
Es kann auch von Vorteil sein, die Verbindungen der Formel I in Kombination mit Sa- fenern zu verwenden. Safener sind chemische Verbindungen, die Schaden an Nutzpflanzen verhindern oder reduzieren, ohne die herbizide Wirkung der Verbindungen der Formel I auf unerwünschte Pflanzen wesentlich zu beeinflussen. Sie können so- wohl vor der Aussaat (beispielsweise bei Saatgutbehandlungen, bei Stecklingen oder Setzlingen) als auch im Vor- oder Nachauflauf der Nutzpflanze verwendet werden. Die Safener und die Verbindungen der Formel I können gleichzeitig oder nacheinander verwendet werden. Geeignete Safener sind beispielsweise (Chinolin-δ-oxy)essig- säuren, 1-Phenyl-5-haloalkyl-1 H-1 ,2,4-triazol-3-carbonsäuren, 1-Phenyl-4,5-dihydro-5- alkyl-1 H-pyrazol-3,5-dicarbonsäuren, 4,5-Dihydro-5,5-diaryl-3-isoxazolcarbonsäuren, Dichloroacetamide, alpha-Oximinophenylacetonitrile, Acetophenonoxime, 4,6-Dihalo-2- phenylpyrimidine, N-[[4-(Aminocarbonyl)phenyl]sulfonyl]-2-benzoesäureamide, 1 ,8- Naphthalsäureanhydrid, 2-Halo-4-(haloalkyl)-5-thiazolcarbonsäuren, Phosphorthiolate und N-Alkyl-O-phenylcarbamate sowie ihre landwirtschaftlich brauchbaren Salze, und vorausgesetzt sie haben eine Säurefunktion, ihre landwirtschaftlich brauchbaren Derivate, wie Amide, Ester und Thioester.It may also be advantageous to use the compounds of the formula I in combination with safeners. Safeners are chemical compounds that prevent or reduce damage to crops without significantly affecting the herbicidal activity of the compounds of formula I on undesirable plants. You can probably before sowing (for example in seed treatments, cuttings or seedlings) as well as in the pre or postemergence of the crop can be used. The safeners and the compounds of formula I can be used simultaneously or sequentially. Suitable safeners are, for example, (quinoline-δ-oxy) acetic acids, 1-phenyl-5-haloalkyl-1H-1, 2,4-triazole-3-carboxylic acids, 1-phenyl-4,5-dihydro-5 alkyl-1H-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-benzoic acid amides, 1,8-naphthalic anhydride, 2-halo-4- (haloalkyl) -5-thiazolecarboxylic acids, phosphorothiolates and N-alkyl-O-phenylcarbamates and their agriculturally useful salts, and provided they have an acid function, their agriculturally useful derivatives such as amides, esters and thioesters.
Zur Verbreiterung des Wirkungsspektrums und zur Erzielung synergistischer Effekte können die Verbindungen der Formel I mit zahlreichen Vertretern anderer herbizider oder wachstumsregulierender Wirkstoffgruppen oder mit Safenern gemischt und gemeinsam ausgebracht werden. Beispielsweise kommen als Mischungspartner 1 ,2,4- Thiadiazole, 1 ,3,4-Thiadiazole, Amide, Aminophosphorsäure und deren Derivate, Ami- notriazole, Anilide, Aryloxy-/Heteroaryloxyalkansäuren und deren Derivate, Benzoesäure und deren Derivate, Benzothiadiazinone, 2-(Hetaroyl/Aroyl)-1 ,3-cyclohexandione, Heteroaryl-Aryl-Ketone, Benzylisoxazolidinone, meta-CF3-Phenylderivate, Carbamate, Chinolincarbonsäure und deren Derivate, Chloracetanilide, Cyclohexenonoximetherde- rivate, Diazine, Dichlorpropionsäure und deren Derivate, Dihydrobenzofurane, Dihydro- furan-3-one, Dinitroaniline, Dinitrophenole, Diphenylether, Dipyridyle, Halogencarbonsäuren und deren Derivate, Harnstoffe, 3-Phenyluracile, Imidazole, Imidazolinone, N- Phenyl-3,4,5,6-tetrahydrophthalimide, Oxadiazole, Oxirane, Phenole, Aryloxy- und He- teroaryloxyphenoxypropionsäureester, Phenylessigsäure und deren Derivate, 2-Phe- nylpropionsäure und deren Derivate, Pyrazole, Phenylpyrazole, Pyridazine, Pyridincar- bonsäure und deren Derivate, Pyrimidylether, Sulfonamide, Sulfonylharnstoffe, Triazi- ne, Triazinone, Triazolinone, Triazolcarboxamide, Uracile sowie Phenylpyrazoline und Isoxazoline und deren Derivate in Betracht.To widen the spectrum of action and to achieve synergistic effects, the compounds of formula I can be mixed with numerous representatives of other herbicidal or growth-regulating active ingredient groups or with safeners and applied together. For example, 1, 2,4-thiadiazoles, 1, 3,4-thiadiazoles, amides, aminophosphoric acid and derivatives thereof, aminotriazoles, anilides, aryloxy / heteroaryloxyalkanoic acids and their derivatives, benzoic acid and derivatives thereof, benzothiadiazinones, (Hetaroyl / aroyl) -1, 3-cyclohexanediones, heteroaryl-aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinolinecarboxylic acid and derivatives thereof, chloroacetanilides, cyclohexenone oxime ether derivatives, diazines, dichloropropionic acid and its derivatives, dihydrobenzofurans, dihydroxy furan-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 acid esters, phenylacetic acid and its derivatives, 2-phenylpropionic acid and derivatives thereof, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and their derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides, uracils and also phenylpyrazolines and isoxazolines and derivatives thereof.
Außerdem kann es von Nutzen sein, die Verbindungen I allein oder in Kombination mit anderen Herbiziden oder auch noch mit weiteren Pflanzenschutzmitteln gemischt, gemeinsam auszubringen, beispielsweise mit Mitteln zur Bekämpfung von Schädlingen oder phytopathogenen Pilzen bzw. Bakterien. Von Interesse ist ferner die Mischbarkeit mit Mineralsalzlösungen, welche zur Behebung von Ernährungs- und Spurenelementmängeln eingesetzt werden. Es können auch weitere Additve wie nicht phytotoxische Öle und Ölkonzentrate zugesetzt werden.In addition, it may be useful to use the compounds I alone or in combination with other herbicides or even mixed with other crop protection agents, together, for example, with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are used for the elimination of nutritional and trace element deficiencies. Other additives such as non-phytotoxic oils and oil concentrates may also be added.
Beispiele für Herbizide, die in Kombination mit den Pyridinverbindungen der Formel I gemäß der vorliegenden Erfindung verwendet werden können, sind: b1) aus der Gruppe der Lipid-Biosynthese-Inhibitoren:Examples of herbicides that can be used in combination with the pyridine compounds of the formula I according to the present invention are: b1) from the group of lipid biosynthesis inhibitors:
Alloxydim, Alloxyd im-natrium, Butroxydim, Clethodim, Clodinafop, Clodinafop-propar- gyl, Cycloxydim, Cyhalofop, Cyhalofop-butyl, Diclofop, Diclofop-methyl, Fenoxaprop, Fenoxaprop-ethyl, Fenoxaprop-P, Fenoxaprop-P-ethyl, Fluazifop, Fluazifop-butyl, FIu- azifop-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, Benfuresat, Butylat, Cycloat, Dalapon, Dime- piperat, EPTC, Esprocarb, Ethofumesat, Flupropanat, Molinat, Orbencarb, Pebulat, Prosulfocarb, TCA, Thiobencarb, Tiocarbazil, Triallat und Vernolat; b2) aus der Gruppe der ALS-Inhibitoren: Amidosulfuron, Azimsulfuron, Bensulfuron, Bensulfuron-methyl, Bispyribac, Bispyribac- natrium, Chlorimuron, Chlorimuron-ethyl, Chlorsulfuron, Cinosulfuron, Cloransulam, Cloransulam-methyl, Cyclosulfamuron, Diclosulam, Ethametsulfuron, Ethametsulfuron- methyl, Ethoxysulfuron, Flazasulfuron, Florasulam, Flucarbazon, Flucarbazon-natrium, Flucetosulfuron, Flumetsulam, Flupyrsulfuron, Flupyrsulfuron-methyl-natrium, Foram- sulfuron, Halosulfuron, Halosulfuron-methyl, Imazamethabenz, Imazamethabenz- methyl, Imazamox, Imazapic, Imazapyr, Imazaquin, Imazethapyr, Imazosulfuron, lodo- sulfuron, lodosulfuron-methyl-natrium, Mesosulfuron, Metosulam, Metsulfuron, Metsul- furon-methyl, Nicosulfuron, Orthosulfamuron, Oxasulfuron, Penoxsulam, Primisulfuron, Primisulfuron-methyl, Propoxycarbazon, Propoxycarbazon-natrium, Prosulfuron, Pyra- zosulfuron, Pyrazosulfuron-ethyl, Pyribenzoxim, Pyrimisulfan, Pyriftalid, Pyriminobac, Pyriminobac-methyl, Pyrithiobac, Pyrithiobac-natrium, Pyroxsulam, Rimsulfuron, SuI- fometuron, Sulfometuron-methyl, Sulfosulfuron, Thiencarbazon, Thiencarbazon-methyl, Thifensulfuron, Thifensulfuron-methyl, Triasulfuron, Tribenuron, Tribenuron-methyl, Trifloxysulfuron, Triflusulfuron, Triflusulfuron-methyl und Tritosulfuron; b3) aus der Gruppe der Photosynthese-Inhibitoren: Ametryn, Amicarbazon, Atrazin, Bentazon, Bentazon-natrium, Bromacil, Bromofeno- xim, Bromoxynil und seine Salze und Ester, Chlorobromuron, Chloridazon, Chlorotolu- ron, Chloroxuron, Cyanazin, Desmedipham, Desmetryn, Dimefuron, Dimethametryn, Diquat, Diquat-dibromid, Diuron, Fluometuron, Hexazinon, loxynil und seine Salze und Ester, Isoproturon, Isouron, Karbutilat, Lenacil, Linuron, Metamitron, Methabenzthiazu- ron, Metobenzuron, Metoxuron, Metribuzin, Monolinuron, Neburon, Paraquat, Para- quat-dichlorid, Paraquat-dimetilsulfat, Pentanochlor, Phenmedipham, Phenmedipham- ethyl, Prometon, Prometryn, Propanil, Propazin, Pyridafol, Pyridat, Siduron, Simazin, Simetryn, Tebuthiuron, Terbacil, Terbumeton, Terbuthylazin, Terbutryn, Thidiazuron und Trietazin; b4) aus der Gruppe der Protoporphyrinogen-IX-Oxidase-Inhibitoren:Alloxydim, alloxide in sodium, butroxydim, clethodim, clodinafop, clodinafop-propargyl, cycloxydim, cyhalofop, cyhalofop-butyl, diclofop, diclofop-methyl, fenoxaprop, Fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop-butyl, fluc-a-stop P, fluazifop-p-butyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-methyl, metamifop, Pinoxaden, Profoxydim, Propaquizafop, Quizalofop, Quizalofopethyl, Quizalofop-tefuryl, Quizalofop-P, Quizalofop-P-ethyl, Quizalofop-P-tefuryl, Sethoxydim, Tepraloxydim, Tralkoxydim, Benfuresat, Butylate, Cycloat, Dalapon, Dimepiperate, EPTC, esprocarb, ethofumesate, flupropanate, molinate, orbencarb, pebulate, prosulfocarb, TCA, thiobencarb, tiocarbazil, triallate and vernolate; b2) from the group of ALS inhibitors: amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, bispyribac, bispyribac-sodium, chlorimuron, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, cloransulam, cloransulam-methyl, cyclosulfamuron, diclosulam, ethametsulfuron, ethametsulfuron methyl, ethoxysulfuron, flazasulfuron, florasulam, flucarbazone, flucarbazone sodium, flucetosulfuron, flumetsulam, flupyrsulfuron, flupyrsulfuron-methyl-sodium, foramysulfuron, 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, pyra- zosulfuron, pyrazosulfuron-ethyl, pyribenzoxime, pyrimisulfan, pyriftalid, pyriminobac, pyriminobac-methyl, pyrithiobac, pyrith iobac-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 photosynthesis inhibitors: ametryn, amicarbazone, atrazine, bentazone, bentazone sodium, bromacil, bromofenoxime, bromoxynil and its salts and esters, chlorobromuron, chloridazon, chlorotoluron, chloroxuron, cyanazine, desmedipham, desmetryn , Dimefuron, dimethametryn, diquat, diquat-dibromide, diuron, fluometuron, hexazinone, loxynil and its salts and esters, isoproturon, isourone, carbutilate, lenacil, linuron, metamitron, methabenzthiazirone, metobenzuron, metoxuron, metribuzin, monolinuron, neburon, Paraquat, paraquat-dichloride, paraquat-dimetilsulfate, pentanochlor, phenmedipham, phenmediphamethyl, prometon, prometryn, propanil, propazine, pyridafol, pyridate, siduron, simazine, simetryn, tebuthiuron, terbacil, terbumetone, terbuthylazine, terbutryn, thidiazuron and trietazine; b4) from the group of protoporphyrinogen IX oxidase inhibitors:
Acifluorfen, Acifluorfen-natrium, Azafenidin, Bencarbazon, Benzfendizon, Bifenox, Bu- tafenacil, Carfentrazon, Carfentrazon-ethyl, Chlomethoxyfen, Cinidon-ethyl, Fluazolat, Flufenpyr, Flufenpyr-ethyl, Flumiclorac, Flumiclorac-pentyl, Flumioxazin, Fluoroglyco- fen, Fluoroglycofen-ethyl, Fluthiacet, Fluthiacet-methyl, Fomesafen, Halosafen, Lacto- fen, Oxadiargyl, Oxadiazon, Oxyfluorfen, Pentoxazon, Profluazol, Pyraclonil, Pyraflu- fen, Pyraflufen-ethyl, Saflufenacil, Sulfentrazon, Thidiazimin, 2-Chlor-5-[3,6-dihydro-3- methyl-2,6-dioxo-4-(trifluormethyl)-1 (2H)-pyrimidinyl]-4-fluor-N-[(isopropyl)methylsulf- amoyl]benzamid (B-1 ; CAS 372137-35-4), [3-[2-Chlor-4-fluor-5-(1-methyl-6-trifluor- methyl-2,4-dioxo-1 ,2,3,4,-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]essigsäure- ethylester (B-2; CAS 353292-31-6), N-Ethyl-3-(2,6-dichlor-4-trifluormethylphenoxy)-5- methyl-1 H-pyrazol-1-carboxamid (B-3; CAS 452098-92-9), N-Tetrahydrofurfuryl-3-(2,6- dichlor-4-trifluormethylphenoxy)-5-methyl-1 H-pyrazol-1-carboxamid (B-4; CAS 915396- 43-9), N-Ethyl-3-(2-chlor-6-fluor-4-trifluormethylphenoxy)-5-methyl-1 H-pyrazol-1 -carb- oxamid (B-5; CAS 452099-05-7) und N-Tetrahydrofurfuryl-3-(2-chlor-6-fluor-4-trifluor- methylphenoxy)-5-methyl-1 H-pyrazol-1 -carboxamid (B-6; CAS 45100-03-7); b5) aus der Gruppe der Bleacher-Herbizide: Aclonifen, Amitrol, Beflubutamid, Benzobicyclon, Benzofenap, Clomazon, Diflufeni- can, Fluridon, Flurochloridon, Flurtamon, Isoxaflutol, Mesotrion, Norflurazon, Picolina- fen, Pyrasulfutol, Pyrazolynat, Pyrazoxyfen, Sulcotrion, Tefuryltrion, Tembotrion, Top- ramezon, 4-Hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluormethyl)-3-pyridyl]car- bonyl]bicyclo[3.2.1]oct-3-en-2-one (B-7; CAS 352010-68-5) und 4-(3-Trifluormethyl- phenoxy)-2-(4-trifluormethylphenyl)pyrimidin (B-8; CAS 180608-33-7); b6) aus der Gruppe der EPSP-Synthase-lnhibitoren: Glyphosat, Glyphosat-isopropylammonium und Glyphosat-trimesium (Sulfosat); b7) aus der Gruppe der Glutamin-Synthase-Inhibitoren:Acifluorfen, acifluorfen sodium, azafenidine, bencarbazone, benzfendizone, bifenox, buafenacil, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, cinidone-ethyl, fluazolate, flufenpyr, flufenpyr-ethyl, flumiclorac, flumiclorac-pentyl, flumioxazine, fluoroglycofene, Fluoroglycofen-ethyl, Fluthiacet, Fluthiacet-methyl, Fomesafen, Halosafen, Lactofen, Oxadiargyl, Oxadiazon, Oxyfluorfen, Pentoxazone, Profluazole, Pyraclonil, Pyrafluene, 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) -methylsulfonate] amoyl] benzamide (B-1; CAS 372137-35-4), [3- [2-chloro-4-fluoro-5- (1-methyl-6-trifluoromethyl-2,4-dioxo-1,2-yl) , 3,4-tetrahydropyrimidin-3-yl) phenoxy] -2-pyridyloxy] acetic acid ethyl ester (B-2; CAS 353292-31-6), N-ethyl-3- (2,6-dichloro-4-) trifluoromethylphenoxy) -5-methyl-1H-pyrazole-1-carboxamide (B-3; CAS 452098-92-9), N-tetrahydrofurfuryl-3- (2,6-dichloro-4-trifluoromethylphenoxy) -5-methyl- 1 H-pyrazole-1-carboxamide (B-4; CAS 915396-43-9), N-ethyl-3- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) -5-methyl-1H-pyrazole 1-carboxamide (B-5; CAS 452099-05-7) and N-tetrahydrofurfuryl-3- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) -5-methyl-1H-pyrazole-1 carboxamide (B-6; CAS 45100-03-7); b5) from the group of bleacher herbicides: aclonifen, amitrole, beflubutamide, benzobicyclone, benzofenap, clomazone, difluufenican, fluridone, flurochloridone, flurtamone, isoxaflutole, mesotrione, norflurazon, picolinefine, pyrasulfutole, pyrazolynate, pyrazoxyfen, sulcotrione, Tefuryltrione, tembotrione, topramame, 4-hydroxy-3 - [[2 - [(2-methoxyethoxy) methyl] -6- (trifluoromethyl) -3-pyridyl] carbonyl] bicyclo [3.2.1] oct-3 -en-2-one (B-7; CAS 352010-68-5) and 4- (3-trifluoromethylphenoxy) -2- (4-trifluoromethylphenyl) pyrimidine (B-8; CAS 180608-33-7); b6) from the group of EPSP synthase inhibitors: glyphosate, glyphosate isopropylammonium and glyphosate trimesium (sulfosate); b7) from the group of glutamine synthase inhibitors:
Bilanaphos (Bialaphos), Bilanaphos-natrium, Glufosinat und Glufosinat-ammonium; b8) aus der Gruppe der DHP-Synthase-Inhibitoren: Asulam; b9) aus der Gruppe der Mitose-Inhibitoren:Bilanaphos (bialaphos), bilanaphos-sodium, glufosinate and glufosinate-ammonium; b8) from the group of DHP synthase inhibitors: asulam; b9) from the group of mitosis inhibitors:
Amiprophos, Amiprophos-methyl, Benfluralin, Butamiphos, Butralin, Carbetamid, Chlorpropham, Chlorthal, Chlorthal-dimethyl, Dinitramin, Dithiopyr, Ethalfluralin, FIu- chloralin, Oryzalin, Pendimethalin, Prodiamin, Propham, Propyzamid, Tebutam, Thia- zopyr und Trifluralin; b10) aus der Gruppe der VLCFA-lnhibitoren:Amiprophos, Amiprophos-methyl, Benfluralin, Butamiphos, Butraline, Carbetamide, Chlorpropham, Chlorthal, Chlorthal-dimethyl, Dinitramine, Dithiopyr, Ethalfluralin, Flu chlorin, Oryzalin, Pendimethalin, Prodiamine, Propham, Propyzamide, Tebutam, Thiazopyr and Trifluralin; b10) from the group of VLCFA inhibitors:
Acetochlor, Alachlor, Anilofos, Butachlor, Cafenstrol, Dimethachlor, Dimethanamid, Dimethenamid-P, Diphenamid, Fentrazamid, Flufenacet, Mefenacet, Metazachlor, Me- tolachlor, Metolachlor-S, Naproanilid, Napropamid, Pethoxamid, Piperophos, Pretila- chlor, Propachlor, Propisochlor, Pyroxasulfon (KIH-485) und Thenylchlor;Acetochlor, Alachlor, Anilofos, Butachlor, Cafenstrol, Dimethachlor, Dimethanamide, Dimethenamid-P, Diphenamid, Fentrazamide, Flufenacet, Mefenacet, Metazachlor, Metolachlor, Metolachlor-S, Naproanilide, Napropamide, Pethoxamide, Piperophos, Pretilochlor, Propachlor, Propisochlor, Pyroxasulfone (KIH-485) and Thenylchlor;
Verbindungen der Formel 2:Compounds of the formula 2:
worin die Variablen folgende Bedeutungen haben: wherein the variables have the following meanings:
Y Phenyl oder 5- oder 6-gliedriges Heteroaryl wie eingangs definiert, welche durch eine bis drei Gruppen Raa substituiert sein können; R21, R22, R23, R24 H, Halogen, oder Ci-C4-Alkyl; X O oder NH; n 0 oder 1.Y is phenyl or 5- or 6-membered heteroaryl as defined above, which may be substituted by one to three groups R aa ; R 21 , R 22 , R 23 , R 24 are H, halogen, or C 1 -C 4 -alkyl; X is O or NH; n 0 or 1.
Verbindungen der Formel 2 weisen insbesondere die folgenden Bedeutungen auf: wobei # die Bindung zu dem Molekülgerüst bedeutet; undIn particular, compounds of the formula 2 have the following meanings: where # is the bond to the molecular skeleton; and
R 2i i R 22 R 23 R 24 H i c^ F oder CH3; R25 Halogen, d-C4-Alkyl oder Ci-C4-Haloalkyl; R26 Ci-C4-Alkyl; R27 Halogen, Ci-C4-Alkoxy oder Ci-C4-Haloalkoxy; R28 H, Halogen, Ci-C4- Alkyl, Ci-C4-Haloalkyl oder Ci-C4-Haloalkoxy; m 0, 1 , 2 oder 3; X Sauerstoff; n 0 oder 1. R 2i i R 22 R 23 R 24 H i c ^ F o of CH 3 ; R 25 is halogen, C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl; R 26 is C 1 -C 4 -alkyl; R 27 is halogen, C 1 -C 4 -alkoxy or C 1 -C 4 -haloalkoxy; R 28 is H, halogen, Ci-C 4 - alkyl, Ci-C 4 haloalkyl or Ci-C4-haloalkoxy; m is 0, 1, 2 or 3; X oxygen; n 0 or 1.
Bevorzugte Verbindungen der Formel 2 weisen folgende Bedeutungen auf: ',3 Preferred compounds of the formula 2 have the following meanings: ', 3
R21 H; R22, R23 F; R24 H oder F; X Sauerstoff; n 0 oder 1. Besonders bevorzugte Verbindungen der Formel 2 sind:R 21 H; R 22, R 23 F; R 24 H or F; X oxygen; n is 0 or 1. Particularly preferred compounds of the formula 2 are:
3-[5-(2,2-Difluor-ethoxy)-1-methyl-3-trifluormethyl-1 H-pyrazol-4-ylmethansulfonyl]-4- fluor-5,5-dimethyl-4,5-dihydro-isoxazol (2-1 ); 3-{[5-(2,2-Difluor-ethoxy)-1 -methyl-3-tri- fluormethyl-1 H-pyrazol-4-yl]-fluor-methansulfonyl}-5,5-dimethyl-4,5-dihydro-isoxazol (2-2); 4-(4-Fluor-5,5-dimethyl-4,5-dihydro-isoxazol-3-sulfonylmethyl)-2-methyl-5-trifluor- methyl-2H-[1 ,2,3]triazol (2-3); 4-[(5,5-Dimethyl-4,5-dihydro-isoxazol-3-sulfonyl)-fluor- methyl]-2-methyl-5-trifluormethyl-2H-[1 ,2,3]triazol (2-4); 4-(5,5-Dimethyl-4,5-dihydro- isoxazol-3-sulfonylmethyl)-2-methyl-5-trifluormethyl-2H-[1 ,2,3]triazol (2-5); 3-{[5-(2,2- Difluor-ethoxy)-1-methyl-3-trifluormethyl-1 H-pyrazol-4-yl]-difluor-methansulfonyl}-5,5- dimethyl-4,5-dihydro-isoxazol (2-6); 4-[(5,5-Dimethyl-4,5-dihydro-isoxazol-3-sulfonyl)- difluor-methyl]-2-methyl-5-trifluormethyl-2H-[1 ,2,3]triazol (2-7); 3-{[5-(2,2-Difluor- ethoxy)-1-methyl-3-trifluormethyl-1 H-pyrazol-4-yl]-difluor-methansulfonyl}-4-fluor-5,5- dimethyl-4,5-dihydro-isoxazol (2-8); 4-[Difluor-(4-fluor-5,5-dimethyl-4,5-dihydro-isoxa- zol-3-sulfonyl)-methyl]-2-methyl-5-trifluormethyl-2H-[1 ,2,3]triazol (2-9); 3-[(5-Difluor- methoxy-1-methyl-3-trifluormethyl-1 H-pyrazol-4-yl)-difluor-methansulfonyl]-5,5-di- methyl-4,5-dihydro-isoxazol (2-10); b1 1) aus der Gruppe der Cellulose-Biosynthese-Inhibitoren: Chlorthiamid, Dichlobenil, Flupoxam und Isoxaben; b12) aus der Gruppe der Entkoppler-Herbizide: Dinoseb, Dinoterb und DNOC und seine Salze; b13) aus der Gruppe der Auxin-Herbizide:3- [5- (2,2-Difluoroethoxy) -1-methyl-3-trifluoromethyl-1H-pyrazol-4-ylmethanesulfonyl] -4-fluoro-5,5-dimethyl-4,5-dihydro-isoxazole (2-1); 3 - {[5- (2,2-Difluoroethoxy) -1-methyl-3-trifluoromethyl-1H-pyrazol-4-yl] -fluoro-methanesulfonyl} -5,5-dimethyl-4,5 dihydro-isoxazole (2-2); 4- (4-Fluoro-5,5-dimethyl-4,5-dihydroisoxazol-3-sulfonylmethyl) -2-methyl-5-trifluoromethyl-2H- [1,2,3] triazole (2-3 ); 4 - [(5,5-dimethyl-4,5-dihydroisoxazol-3-sulfonyl) fluoromethyl] -2-methyl-5-trifluoromethyl-2H- [1,2,3] triazole (2-4 ); 4- (5,5-dimethyl-4,5-dihydroisoxazol-3-sulfonylmethyl) -2-methyl-5-trifluoromethyl-2H- [1,2,3] triazole (2-5); 3 - {[5- (2,2-Difluoroethoxy) -1-methyl-3-trifluoromethyl-1H-pyrazol-4-yl] -difluoro-methanesulfonyl} -5,5-dimethyl-4,5-dihydro -isoxazole (2-6); 4 - [(5,5-Dimethyl-4,5-dihydro-isoxazol-3-sulfonyl) -difluoro-methyl] -2-methyl-5-trifluoromethyl-2H- [1,2,3] triazole (2-7 ); 3 - {[5- (2,2-difluoroethoxy) -1-methyl-3-trifluoromethyl-1H-pyrazol-4-yl] difluoro-methanesulfonyl} -4-fluoro-5,5-dimethyl-4 , 5-dihydroisoxazole (2-8); 4- [Difluoro (4-fluoro-5,5-dimethyl-4,5-dihydro-isoxazole-3-sulfonyl) -methyl] -2-methyl-5-trifluoromethyl-2H- [1, 2,3 ] triazole (2-9); 3 - [(5-difluoromethoxy-1-methyl-3-trifluoromethyl-1H-pyrazol-4-yl) difluoro-methanesulfonyl] -5,5-dimethyl-4,5-dihydroisoxazole (2 -10); b1 1) from the group of cellulose biosynthesis inhibitors: chlorthiamide, dichlobenil, flupoxam and isoxaben; b12) from the group of decoupling herbicides: dinoseb, dinoterb and DNOC and its salts; b13) from the group of auxin herbicides:
2,4-D und seine Salze und Ester, 2,4-DB und seine Salze und Ester, Aminopyralid und seine Salze wie Aminopyralid-tris(2-hydroxypropyl)ammonium und seine Ester, Benazolin, Benazolin-ethyl, Chloramben und seine Salze und Ester, Clomeprop, Clopy- ralid und seine Salze und Ester, Dicamba und seine Salze und Ester, Dichlorprop und seine Salze und Ester, Dichlorprop-P und seine Salze und Ester, Fluroxypyr, Fluroxy- pyr-butometyl, Fluroxypyr-meptyl, MCPA und seine Salze und Ester, MCPA-thioethyl, MCPB und seine Salze und Ester, Mecoprop und seine Salze und Ester, Mecoprop-P und seine Salze und Ester, Picloram und seine Salze und Ester, Quinclorac, Quinme- rac, TBA (2,3,6) und seine Salze und Ester, Triclopyr und seine Salze und Ester, und 5,6-Dichlor-2-cyclopropyl-4-pyrimidincarbonsäure (B-9; CAS 858956-08-8) und seine Salze und Ester; b14) aus der Gruppe der Auxin-Transport-Inhibitoren: Diflufenzopyr, Diflufenzopyr- natrium, Naptalam und Naptalam-natrium; b15) aus der Gruppe der sonstigen Herbizide: Bromobutid, Chlorflurenol, Chlor- flurenol-methyl, Cinmethylin, Cumyluron, Dalapon, Dazomet, Difenzoquat, Difenzo- quat-metilsulfate, Dimethipin, DSMA, Dymron, Endothal und seine Salze, Etobenzanid, Flamprop, Flamprop-isopropyl, Flamprop-methyl Flamprop-M-isopropyl, Flamprop-M- methyl, Flurenol, Flurenol-butyl, Flurprimidol, Fosamin, Fosamine-ammonium, Indano- fan, Maleinsäure-hydrazid, Mefluidid, Metam, Methylazid, Methylbromid, Methyl-dym- ron, Methyljodid. MSMA, Ölsäure, Oxaziclomefon, Pelargonsäure, Pyributicarb, Quino- clamin, Triaziflam, Tridiphan und 6-Chlor-3-(2-cyclopropyl-6-methylphenoxy)-4-pyrida- zinol (B-10; CAS 499223-49-3) und seine Salze und Ester.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, benazoline, benazolin-ethyl, chloroamben 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, quineme-rac, TBA (2,3,6) and its salts and esters, Triclopyr and its salts and esters, and 5,6-dichloro-2-cyclopropyl-4-pyrimidinecarboxylic acid (B-9; CAS 858956-08-8) and its salts and esters; b14) from the group of auxin transport inhibitors: diflufenzopyr, diflufenzopyrsodium, naptalam and naptalam sodium; b15) from the group of the other herbicides: bromobutide, chlorofluorol, chlorofluorolmethyl, cinmethylin, cumyluron, dalapon, dazomet, difenzoquat, difenzoquat-metylsulfates, dimethipine, DSMA, dymron, endothal and its salts, etobenzanide, flamprop, Flamprop-isopropyl, Flamprop-methyl Flamprop-M-isopropyl, Flamprop-M-methyl, Flurenol, Flurenol-butyl, Flurprimidol, Fosamine, Fosamine-ammonium, Indano fan, maleic hydrazide, Mefluidide, Metam, methyl azide, methyl bromide, methyl -dymron, methyl iodide. MSMA, oleic acid, oxaziclomefon, pelargonic acid, pyributicarb, quinoclamin, triaziflam, tridiphan and 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol (B-10; CAS 499223-49-3 ) and its salts and esters.
Beispiele für bevorzugte Safener C sind Benoxacor, Cloquintocet, Cyometrinil, Cy- prosulfamid, Dichlormid, Dicyclonon, Dietholate, Fenchlorazol, Fenclorim, Flurazol, FIu- xofenim, Furilazol, Isoxadifen, Mefenpyr, Mephenat, Naphthalsäureanhydrid, Oxabetri- nil, 4-(Dichloracetyl)-1 -oxa-4-azaspiro[4.5]decan (B-1 1 ; MON4660, CAS 71526-07-3) und 2,2,5-Trimethyl-3-(dichloracetyl)-1 ,3-oxazolidin (B-12; R-29148, CAS 52836-31-4). Die Wirkstoffe der Gruppen b1 ) bis b15) und die Safener C sind bekannte Herbizide und Safener, siehe z. B. The Compendium of Pesticide Common Names (http://vvww.alanwood.net/pesticides/); B. Hock, C. Fedtke, R. R. Schmidt, Herbizide, Georg Thieme Verlag, Stuttgart 1995. Weitere herbizide Wirkstoffe sind aus WO 96/26202, WO 97/411 16, WO 97/41 117, WO 97/411 18, WO 01/83459 und WO 2008/074991 sowie aus W. Krämer et al. (ed.) "Modern Crop Protection Compounds", Vol. 1 , Wiley VCH, 2007 und der darin zitierten Literatur bekannt.Examples of preferred safeners C are Benoxacor, Cloquintocet, Cyometrinil, Cyprusulfamide, Dichlormid, Dicyclonon, Dietholate, Fenchlorazole, Fenclorim, Flurazole, Fluxofenim, Furilazole, Isoxadifen, Mefenpyr, Mephenate, Naphthalic Anhydride, Oxabetrinile, 4- (Dichloroacetyl ) -1-oxa-4-azaspiro [4.5] decane (B-1 1; MON4660, CAS 71526-07-3) and 2,2,5-trimethyl-3- (dichloroacetyl) -1,3-oxazolidine (B -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, US Pat. B. The Compendium of Pesticide Common Names (http://www.alanwood.net/pesticides/); B. Hock, C. Fedtke, RR Schmidt, herbicides, Georg Thieme Verlag, Stuttgart 1995. Further herbicidal active compounds are known from WO 96/26202, WO 97/411 16, WO 97/41 117, WO 97/411 18, WO 01 / 83459 and WO 2008/074991 and W. Krämer et al. (ed.) "Modern Crop Protection Compounds", Vol. 1, Wiley VCH, 2007 and the literature cited therein.
Die Erfindung betrifft auch Zusammensetzungen in Form eines als 1 -Komponentenzusammensetzung formulierten Pflanzenschutzmittels, enthaltend eine Wirkstoffkombination, die wenigstens eine Pyridinverbindung der Formel I und wenigstens einen weiteren Wirkstoff, bevorzugt ausgewählt aus den Wirkstoffen der Gruppen b1 bis b15, und wenigstens einen festen oder flüssigen Träger und/oder eine oder mehrere grenz- flächenaktive Substanzen und gewünschtenfalls einen oder mehrere für Pflanzenschutzmittel übliche weitere Hilfsstoffe.The invention also relates to compositions in the form of a crop protection agent formulated as a 1-component composition comprising a combination of active substances comprising at least one pyridine compound of the formula I and at least one further active ingredient, preferably selected from the active substances of groups b1 to b15, and at least one solid or liquid carrier and / or one or more surface-active substances and, if desired, one or more further auxiliaries customary for crop protection agents.
Die Erfindung betrifft auch Zusammensetzungen in Form eines als 2-Komponenten- zusammensetzung formulierten Pflanzenschutzmittels, umfassend eine erste Komponente, enthaltend wenigstens eine Pyridinverbindung der Formel I, einen festen oder flüssigen Träger und/oder eine oder mehrere grenzflächenaktive Substanzen, und eine zweite Komponente, enthaltend wenigstens einen weiteren Wirkstoff, ausgewählt aus den Wirkstoffen der Gruppen b1 bis b15, einem festen oder flüssigen Träger und/oder eine oder mehrere grenzflächenaktive Substanzen, wobei zusätzlich beide Komponenten auch weitere, für Pflanzenschutzmittel üblichen Hilfsmittel enthalten können.The invention also relates to compositions in the form of a plant 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 surface-active substances, and a second component containing at least one further active ingredient selected from the active compounds of groups b1 to b15, a solid or liquid carrier and / or one or more surface-active substances, wherein in addition both components may also contain other, customary for crop protection agents.
In binären Zusammensetzungen, die wenigstens eine Verbindung der Formel I als Komponente A und wenigstens ein Herbizid B enthalten, liegt das Gewichtsverhältnis der Wirkstoffe A:B in der Regel im Bereich von 1 :1000 bis 1000:1 , vorzugsweise im Bereich von 1 :500 bis 500:1 , insbesondere im Bereich von 1 :250 bis 250:1 und besonders bevorzugt im Bereich von 1 :75 bis 75:1.In binary compositions containing 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 from 1: 1000 to 1000: 1, preferably in the range from 1: 500 to 500: 1, in particular in the range of 1: 250 to 250: 1 and particularly preferably in the range of 1: 75 to 75: 1.
In binären Zusammensetzungen, die wenigstens eine Verbindung der Formel I als Komponente A und wenigstens einen Safener C enthalten, liegt das Gewichtsverhältnis der Wirkstoffe A:C in der Regel im Bereich von 1 :1000 bis 1000:1 , vorzugsweise im Bereich von 1 :500 bis 500:1 , insbesondere im Bereich von 1 :250 bis 250:1 und besonders bevorzugt im Bereich von 1 :75 bis 75:1.In binary compositions which comprise 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 from 1: 1000 to 1000: 1, preferably in the range from 1: 500 to 500: 1, in particular in the range of 1: 250 to 250: 1 and particularly preferably in the range of 1: 75 to 75: 1.
In ternären Zusammensetzungen, die sowohl wenigstens eine Verbindung der For- mel I als Komponente A, wenigstens ein Herbizid B und wenigstens einen Safener C enthalten, liegen die relativen Gewichtsanteile der Komponenten A:B in der Regel im Bereich von 1 :1000 bis 1000:1 , vorzugsweise im Bereich von 1 :500 bis 500:1 , insbesondere im Bereich von 1 :250 bis 250:1 und besonders bevorzugt im Bereich von 1 :75 bis 75:1 , das Gewichtsverhältnis der Komponente A:C in der Regel im Bereich von 1 :1000 bis 1000:1 , vorzugsweise im Bereich von 1 :500 bis 500:1 , insbesondere im Bereich von 1 :250 bis 250:1 und besonders bevorzugt im Bereich von 1 :75 bis 75:1 , und das Gewichtsverhältnis der Komponenten B:C in der Regel im Bereich von 1 :1000 bis 1000:1 , vorzugsweise im Bereich von 1 :500 bis 500:1 , insbesondere im Bereich von 1 :250 bis 250:1 und besonders bevorzugt im Bereich von 1 :75 bis 75:1. Vorzugs- weise liegt das Gewichtsverhältnis der Komponenten A + B zur Komponente C im Bereich von 1 :500 bis 500:1 , insbesondere im Bereich von 1 :250 bis 250:1 und besonders bevorzugt im Bereich von 1 :75 bis 75:1.In ternary compositions which comprise 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 proportions by weight of the components A: B are generally in the range from 1: 1000 to 1000: 1, preferably in the range of 1: 500 to 500: 1, in particular in the range of 1: 250 to 250: 1 and particularly preferably in the range of 1: 75 to 75: 1, the weight ratio of the component A: C usually in Range of 1: 1000 to 1000: 1, preferably in the range of 1: 500 to 500: 1, in particular in the range of 1: 250 to 250: 1 and more preferably in the range of 1: 75 to 75: 1, and the weight ratio of the components B: C, generally in the range from 1: 1000 to 1000: 1, preferably in the range from 1: 500 to 500: 1, in particular in the range from 1: 250 to 250: 1 and particularly preferably in the range from 1: 75 to 75: 1. The weight ratio of components A + B to component C is preferably in the range from 1: 500 to 500: 1, in particular in the range from 1: 250 to 250: 1 and particularly preferably in the range from 1: 75 to 75: 1.
Beispiele für besonders bevorzugte erfindungsgemäße Zusammensetzungen, enthaltend jeweils eine individualisierte Verbindung der Formel I und einen Mischungs- partner, bzw. eine Mischungspartnerkombination sind in der folgenden Tabelle B angegeben.Examples of particularly preferred compositions according to the invention, containing in each case an individualized compound of the formula I and a mixing partner, or a mixture partner combination are given in the following Table B.
Einer weitere Ausgestaltung der Erfindung betrifft die in der Tabelle B aufgeführten Zusammensetzungen B-1 bis B-1237, wobei jeweils eine Zeile der Tabelle B einer her- biziden Zusammensetzung entspricht, umfassend eine in der vorliegenden Beschrei- bung individualisierten Verbindungen der Formel I (Komponente 1) und den jeweils in der betreffenden Zeile angegebenen weiteren Wirkstoff aus den Gruppen b1 ) bis b15) und/oder Safener C (Komponente 2). Die Wirkstoffe in den beschriebenen Zusammensetzungen liegen jeweils vorzugsweise in synergistisch wirksamen Mengen vor.A further embodiment of the invention relates to the compositions B-1 to B-1237 listed in Table B, wherein in each case one row of Table B corresponds to a herbicidal composition comprising an individualized in the present specification compounds of formula I (component 1) and the further active ingredient from groups b1) to b15) and / or safener C (component 2) respectively indicated in the relevant line. The active ingredients in the described compositions are each preferably present in synergistically effective amounts.
Tabelle B: Table B:
Die Verbindungen I und die erfindungsgemäßen Zusammensetzungen können auch eine pflanzenstärkende Wirkung aufweisen. Sie eigenen sich daher zu Mobilisierung pflanzeneigener Abwehrkräfte gegen Befall durch unerwünschte Mikroorganismen, wie Schadpilze, aber auch Viren und Bakterien. Unter pflanzenstärkenden (resistenzinduzierenden) Stoffen sind in diesem Zusammenhang solche Substanzen zu verstehen, die in der Lage sind, das Abwehrsystem von behandelten Pflanzen so zu stimulieren, dass diese bei nachfolgender Inokulation mit unerwünschten Mikroorganismen weitgehende Resistenz gegen diese Mikroorganismen entfalten. Die Verbindungen I können eingesetzt werden, um Pflanzen innerhalb eines gewissen Zeitraumes nach der Behandlung gegen den Befall durch unerwünschte Mikroorganismen zu schützen. Der Zeitraum, innerhalb dessen Schutz herbeigeführt wird, erstreckt sich im Allgemeinen auf 1 bis 28 Tage, vorzugsweise 1 bis 14 Tage nach der Behandlung der Pflanzen mit den Verbindungen I bzw. nach Behandlung des Saatguts, auf bis zu 9 Monate nach Aussaat.The compounds I and the compositions according to the invention may also have a plant-strengthening effect. They are therefore suitable for mobilizing plant-own defenses against infestation by undesirable microorganisms, such as harmful fungi, but also viruses and bacteria. In this context, plant-strengthening (resistance-inducing) substances are to be understood as meaning those substances which are capable of stimulating the defense system of treated plants in such a way that they develop extensive resistance to these microorganisms during subsequent inoculation with undesired microorganisms. The compounds I can be used to protect plants against attack by undesired microorganisms within a certain period of time after the treatment. The period within which protection is provided generally extends from 1 to 28 days, preferably 1 to 14 days after treatment of the plants with the compounds I or after treatment of the seed, up to 9 months after sowing.
Die Verbindungen I und die erfindungsgemäßen Zusammensetzungen eignen sich auch zur Steigerung des Ernteertrages.The compounds I and the compositions according to the invention are also suitable for increasing crop yield.
Sie sind außerdem mindertoxisch und weisen eine gute Pflanzenverträglichkeit auf.They are also low toxicity and have good plant tolerance.
Synthesebeispielesynthesis Examples
Die in den nachstehenden Synthesebeispielen wiedergegebenen Vorschriften wurden unter entsprechender Abwandlung der Ausgangsverbindungen zur Gewinnung weiterer Verbindungen I benutzt. Die so erhaltenen Verbindungen sind in der anschließenden Tabelle mit physikalischen Angaben aufgeführt. The instructions given in the Synthesis Examples below were with appropriate modification of the starting compounds for obtaining further compounds I used. The compounds thus obtained are listed in the following table with physical data.
I. HerstellungsbeispieleI. Preparation Examples
Beispiel 1 : Herstellung von 3-(3-Hydroxy-pyridin-2-yl)-3-oxo-2-(2-trifluormethyl- phenyl)-propionsäuremethylester [1-1 ]Example 1: Preparation of 3- (3-hydroxy-pyridin-2-yl) -3-oxo-2- (2-trifluoromethyl-phenyl) -propionic acid methyl ester [1-1]
Stufe 1 : 3-(4-Methoxy-benzyloxy)-pyridin-2-carbonsäuremethylester Eine Lösung von 15,2g 3-Hydroxy-pyridin-2-methylester in 200 ml Dimethylformamid (DMF) wurde mit 4g NaH versetzt und 30 min bei 20-250C gerührt. Dann wurden 15,4g Para-methoxybenzylchlorid hinzugefügt. Die Mischung wurde bei 400C etwa 15 Std. gerührt und anschließend in Wasser gegeben. Nach Extraktion mit Ethylacetat, Phasentrennung und Waschen der vereinigten organischen Phasen mit Wasser und ges. NaCI-Lösung, dann Trocknen und Entfernen des Lösungsmittels wurde der Rückstand einer Säulenchromatographie unterworfen. Man erhielt 20g der Titelverbindung als gelbes Öl.Step 1: Methyl 3- (4-methoxy-benzyloxy) -pyridine-2-carboxylate A solution of 15.2 g of 3-hydroxy-pyridine-2-methyl ester in 200 ml of dimethylformamide (DMF) was admixed with 4 g NaH and stirred for 20 min -25 0 C stirred. Then, 15.4 g of para-methoxybenzyl chloride was added. The mixture was stirred at 40 ° C. for about 15 hours and then poured into water. After extraction with ethyl acetate, phase separation and washing of the combined organic phases with water and sat. NaCl solution, then drying and removal of the solvent, the residue was subjected to column chromatography. 20 g of the title compound were obtained as a yellow oil.
Stufe 2: 3-(4-Methoxy-benzyloxy)-pyridin-2-carbonsäureStep 2: 3- (4-Methoxy-benzyloxy) -pyridine-2-carboxylic acid
Eine Lösung von 7g des Esters aus Stufe 1 und 2,2g LiOH in 60 ml Methanol und 40ml Wasser wurde bei 20-25°C etwa 15 Std. gerührt. Dann wurden 100 ml Wasser und 7 ml Essigsäure zugegeben. Die Mischung wurde mit Ethylacetat extrahiert. Die verei- ningten organischen Phasen wurden getrocknet und vom Lösungsmittel befreit. Es wurden 5g der Titelverbindung als gelblicher Feststoff erhalten.A solution of 7 g of the ester from stage 1 and 2.2 g of LiOH in 60 ml of methanol and 40 ml of water was stirred at 20-25 ° C for about 15 hours. Then, 100 ml of water and 7 ml of acetic acid were added. The mixture was extracted with ethyl acetate. The combined organic phases were dried and freed from the solvent. 5 g of the title compound were obtained as a yellowish solid.
Stufe 3: 3-(4-Methoxy-benzyloxy)-pyridin-2-carbonsäurepentafluorphenylester Zu einer Lösung von 5g der Säure aus Stufe 2 und 3,5g Pentafluorphenol in 100ml CH2CI2 wurden 2,4g N,N'-Diisopropylcarbodiimid tropfenweise zugesetzt. Die Mischung wurde bei 20-250C etwa 1 Std. gerührt, dann mit ges. NaCI-Lösung gewaschen und im Vakuum eingeengt. Nach säulenchromatographischer Reinigung des Rückstandes (Petrolether: Ethylacetat 5:1 ) wurden 4,6g der Titelverbindung erhalten.Step 3: 3- (4-Methoxy-benzyloxy) -pyridine-2-carboxylic acid pentafluorophenyl ester To a solution of 5 g of the acid from Step 2 and 3.5 g of pentafluorophenol in 100 mL of CH 2 Cl 2 were added 2.4 g of N, N'-diisopropylcarbodiimide dropwise. The mixture was stirred at 20-25 0 C for about 1 hr, then with sat. NaCl solution and concentrated in vacuo. After purification by column chromatography on the residue (petroleum ether: ethyl acetate 5: 1), 4.6 g of the title compound were obtained.
Stufe 4: 3-[3-(4-Methoxy-benzyloxy)-pyridin-2-yl]-3-oxo-2-(2-trifluormethyl-phenyl)- propionsäuremethylesterStep 4: Methyl 3- [3- (4-methoxy-benzyloxy) -pyridin-2-yl] -3-oxo-2- (2-trifluoromethyl-phenyl) -propionate
Zu einer Lösung von 1 ,2g des Esters aus Stufe 3 in 10ml DMF wurden 0,74g Kalium- tert-Butanolat zugegeben. Die Mischung wurde bei 20-25°C etwa 30min gerührt. Anschließend wurde eine Lösung von 2,25g (2-Trifluormethyl-phenyl)-essigsäure- methylester in 5ml DMF zugegeben. Nach 30 min rühren bei 20-25°C wurde die Reaktion durch Zugabe von ges. NH4CI-Lösung beendet. Die Mischung wurde mit Ethylacetat extrahiert. Die vereiningten organischen Phasen wurden mit ges. NaCI-Lösung gewaschen, dann getrocknet und vom Lösungsmittel befreit. Nach säulenchromatographischer Reinigung des Rückstandes (PetroletheπEthylacetat 5:1 ) wurden 0,23g der Titelverbindung erhalten. Stufe 5: 3-(3-Hydroxy-pyridin-2-yl)-3-oxo-2-(2-trifluormethyl-phenyl)-propionsäure- methylesterTo a solution of 1.2 g of the ester from Step 3 in 10 ml of DMF was added 0.74 g of potassium tert-butoxide. The mixture was stirred at 20-25 ° C for about 30 minutes. Subsequently, a solution of 2,25g (2-trifluoromethyl-phenyl) -acetic acid methyl ester in 5 ml of DMF was added. After stirring for 30 min at 20-25 ° C, the reaction by addition of sat. NH4CI solution ended. The mixture was extracted with ethyl acetate. The unified organic phases were washed with sat. NaCl solution, then dried and freed from the solvent. After purification by column chromatography of the residue (petroleum ether ethyl acetate 5: 1), 0.23 g of the title compound were obtained. Step 5: 3- (3-Hydroxy-pyridin-2-yl) -3-oxo-2- (2-trifluoromethyl-phenyl) -propionic acid methyl ester
160mg des Esters aus Stufe 4 wurden mit 1 ml Trifluoressigsäure bei 00C versetzt und die Reaktionsmischung wurde 20 min bei 00C gerührt. Anschließend wurde ges. NaHCθ3-Lösung zugegeben. Nach Extraktion mit Ethylacetat, Entfernen des Lösungsmittels im Vakuum und präparativer HPLC wurden 83mg der Titelverbindung erhalten.160mg of the ester from step 4 were treated with 1 ml of trifluoroacetic acid at 0 0 C and the reaction mixture was stirred for 20 min at 0 0 C. Subsequently, sat. NaHCO 3 solution added. After extraction with ethyl acetate, removal of the solvent in vacuo and preparative HPLC, 83 mg of the title compound were obtained.
1H NMR (CDCI3): δ 1 1 ,05 (brs, 1 H); 8,26-8,24 (m, 1 H); 7,73 (d, 1 H); 7,61-7,58 (m, 2H); 7,48-7,34 (m, 3H); 6,64 (s, 1 H); 3,76 (s, 3H). 1 H NMR (CDCl 3 ): δ 1 1, 05 (brs, 1H); 8.26-8.24 (m, 1H); 7.73 (d, 1H); 7.61-7.58 (m, 2H); 7.48-7.34 (m, 3H); 6.64 (s, 1H); 3.76 (s, 3H).
Beispiel 2: Herstellung von 3-Acetoxy-3-(3-acetoxypyridin-2-yl)-2-(2-trifluormethyl- phenyl)-acrylsäuremethylester [I-2]Example 2 Preparation of 3-acetoxy-3- (3-acetoxypyridin-2-yl) -2- (2-trifluoromethylphenyl) -acrylic Acid Methyl Ester [I-2]
Eine Lösung von 3-Hydroxy-3-(3-hydroxypyridin-2-yl)-2-(2-trifluormethylphenyl)- acrylsäuremethylester (aus Bsp. 1 ) in 5 ml Toluol wurde bei 20 bis 25°C mit 414 mg Acetylchlorid und 210 mg Pyridin versetzt. Die Mischung wurde 2 Std. bei 1000C gerührt. Nach Entfernung des Lösungsmittels im Vakuum wurde eine wäßrige HCI- Lösung hinzugefügt. Nach Extraktion mit Ethylacetat, Waschen mit ges. NaCI-Lösung , Trocknen und Entfernen des Lösungsmittels im Vakuum wurde nach Reinigung durch präparative HPLC 90 mg der Titelverbindung erhalten. A solution of methyl 3-hydroxy-3- (3-hydroxypyridin-2-yl) -2- (2-trifluoromethylphenyl) acrylate (from Ex. 1) in 5 ml of toluene was treated with 414 mg of acetyl chloride at 20-25 ° C 210 mg of pyridine were added. The mixture was stirred at 100 ° C. for 2 hours. After removal of the solvent in vacuo, an aqueous HCl solution was added. After extraction with ethyl acetate, washing with sat. NaCl solution, drying and removal of the solvent in vacuo gave, after purification by preparative HPLC, 90 mg of the title compound.
Tabelle I: Verbindungen der Formel I, welche den Formeln 1.1 A, I.2A, I.1T, bzw. I.2T entsprechen: Table I: Compounds of the formula I which correspond to the formulas 1.1 A, I.2A, I.1T or I.2T:
Anwendungsbeispiele applications
Die herbizide Wirkung der Verbindungen der Formel I ließ sich durch Gewächshausversuche zeigen:The herbicidal activity of the compounds of the formula I was demonstrated by greenhouse experiments:
Als Kulturgefäße dienten Plastiktöpfe mit lehmigem Sand mit etwa 3,0% Humus als Substrat. Die Samen der Testpflanzen wurden nach Arten getrennt eingesät.The culture vessels used were plastic pots with loamy sand with about 3.0% humus as substrate. The seeds of the test plants were sown separately by species.
Bei Vorauflaufbehandlung wurden die in Wasser suspendierten oder emulgierten Wirkstoffe direkt nach Einsaat mittels fein verteilender Düsen aufgebracht. Die Gefäße wurden leicht beregnet, um Keimung und Wachstum zu fördern, und anschließend mit durchsichtigen Plastikhauben abgedeckt, bis die Pflanzen angewachsen waren. Diese Abdeckung bewirkt ein gleichmäßiges Keimen der Testpflanzen, sofern dies nicht durch die Wirkstoffe beeinträchtigt wurde.In pre-emergence treatment, the active ingredients suspended or emulsified in water were applied directly after sowing by means of finely distributing nozzles. The jars were lightly rained to promote germination and growth and then covered with clear plastic hoods until the plants had grown. This cover causes a uniform germination of the test plants, if it was not affected by the active ingredients.
Zum Zweck der Nachauflaufbehandlung wurden die Testpflanzen je nach Wuchsform erst bis zu einer Wuchshöhe von 3 bis 15 cm angezogen und dann mit den in Wasser suspendierten oder emulgierten Wirkstoffen behandelt. Die Testpflanzen wurden dafür entweder direkt gesät und in den gleichen Gefäßen aufgezogen oder sie wurden erst als Keimpflanzen getrennt angezogen und einige Tage vor der Behandlung in die Versuchsgefäße verpflanzt.For the postemergence treatment, the test plants were grown depending on the growth form only to a height of from 3 to 15 cm and then treated with the suspended or emulsified in water agents. For this purpose, the test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and transplanted into the test containers a few days before the treatment.
Die Pflanzen wurden artenspezifisch bei Temperaturen von 10 - 25°C bzw. 20 - 35°C gehalten. Die Versuchsperiode erstreckte sich über 2 bis 4 Wochen. Während dieser Zeit wurden die Pflanzen gepflegt, und ihre Reaktion auf die einzelnen Behandlungen wurde ausgewertet.The plants were kept species-specific at temperatures of 10 - 25 ° C and 20 - 35 ° C, respectively. The trial period lasted for 2 to 4 weeks. During this time, the plants were cared for, and their response to each treatment was evaluated.
Bewertet wurde nach einer Skala von 0 bis 100. Dabei bedeutet 100 kein Aufgang der Pflanzen bzw. völlige Zerstörung zumindest der oberirdischen Teile und 0 keine Schädigung oder normaler Wachstumsverlauf. Eine gute herbizide Aktivität ist bei Werten von wenigstens 70 und eine sehr gute herbizide Aktivität ist bei Werten von wenigstens 85 gegeben.The rating was based on a scale of 0 to 100. 100 means no emergence of the plants or complete destruction of at least the above-ground parts and 0 no damage or normal growth course. A good herbicidal activity is at values of at least 70 and a very good herbicidal activity is given at values of at least 85.
Die in den Gewächshausversuchen verwendeten Pflanzen setzten sich aus folgenden Arten zusammen:The plants used in the greenhouse experiments were composed of the following species:
1 ) Der Wirkstoff 1-1 zeigte bei einer Aufwandmenge von 3,0 kg/ha im Vo rauf I auf gegen ABUTH eine gute und gegen SETIT eine sehr gute herbizide Wirkung.1) The active ingredient 1-1 showed at a rate of 3.0 kg / ha in Iauf on against ABUTH a good and against SETIT a very good herbicidal action.
2) Die Wirkstoffe 1-1 , I-8, bzw. I-9 zeigten bei einer Aufwandmenge von 3,0 kg/ha im Nachauflauf gegen ABUTH eine sehr gute herbizide Wirkung.2) The active compounds 1-1, I-8, and I-9 showed at a rate of 3.0 kg / ha postemergence against ABUTH a very good herbicidal activity.
3) Der Wirkstoff 1-1 zeigte bei einer Aufwandmenge von 3,0 kg/ha im Nachauflauf gegen ALOMY eine gute und der Wirkstoff I-9 eine sehr gute herbizide Wirkung.3) The active ingredient 1-1 showed at a rate of 3.0 kg / ha postemergence against ALOMY a good and the active ingredient I-9 a very good herbicidal activity.
4) Der Wirkstoff 1-1 zeigte bei einer Aufwandmenge von 0,25 kg/ha und die Wirkstoffe I-2, I-3, I-4, I-6*, bzw. I-7 bei 0,5 kg/ha und der Wirkstoff I-5 bei 1 ,0 kg/ha im Nach- auflauf gegen AMARE eine sehr gute herbizide Wirkung.4) The active ingredient 1-1 at an application rate of 0.25 kg / ha and the active ingredients I-2, I-3, I-4, I-6 * , and I-7 at 0.5 kg / ha and the active ingredient I-5 at 1, 0 kg / ha post-emergence against AMARE a very good herbicidal activity.
5) Der Wirkstoff 1-17 zeigte bei einer Aufwandmenge von 1 ,0 kg/ha im Nachauflauf gegen APESV eine sehr gute herbizide Wirkung.5) The active ingredient 1-17 showed at a rate of 1, 0 kg / ha postemergence against APESV a very good herbicidal activity.
6) Die Wirkstoffe 1-1 , bzw. I-8 zeigten bei einer Aufwandmenge von 3,0 kg/ha im Nachauflauf gegen AVEFA eine sehr gute herbizide Wirkung. 7) Der Wirkstoff 1-1 zeigte bei einer Aufwandmenge von 0,25 kg/ha, die Wirkstoffe I-6) The active compounds 1-1, and I-8 showed at a rate of 3.0 kg / ha postemergence against AVEFA a very good herbicidal activity. 7) The active ingredient 1-1 at an application rate of 0.25 kg / ha, the active ingredients I-
2, I-3, I-4, I-6*, bzw. I-7 bei 0,5 kg/ha und der Wirkstoff I-5 bei 1 ,0 kg/ha im Nachauflauf gegen CHEAL eine sehr gute herbizide Wirkung.2, I-3, I-4, I-6 * , and I-7 at 0.5 kg / ha and the active ingredient I-5 at 1, 0 kg / ha postemergence against CHEAL a very good herbicidal activity.
8) Der Wirkstoff 1-17 zeigte bei einer Aufwandmenge von 1 ,0 kg/ha im Nachauflauf gegen CHEAL eine gute herbizide Wirkung. 9) Der Wirkstoff 1-1 zeigte bei einer Aufwandmenge von 0,25 kg/ha im Nachauflauf gegen GALAP eine sehr gute herbizide Wirkung.8) The active ingredient 1-17 showed at a rate of 1, 0 kg / ha postemergence against CHEAL a good herbicidal action. 9) The active ingredient 1-1 showed at a rate of 0.25 kg / ha postemergence against GALAP a very good herbicidal activity.
10) Der Wirkstoff 1-1 zeigte bei einer Aufwandmenge von 3,0 kg/ha im Nachauflauf gegen SETFA eine sehr gute herbizide Wirkung. * Aufwandmenge 0,528 kg/ha 10) The active ingredient 1-1 showed at a rate of 3.0 kg / ha postemergence against SETFA a very good herbicidal activity. * Application rate 0.528 kg / ha

Claims

Patentansprüche: claims:
1. Heterozyklische Verbin I1. heterocyclic verbin I
worin die Variablen folgende Bedeutung haben wherein the variables have the following meaning
R1 OR, SR oder NR1R";R 1 is OR, SR or NR 1 R ";
R Wasserstoff, Ci -C6-Al kyl, Ci-C4-Haloalkyl, C2-C6-Alkenyl, C3-C6-Alki- nyl, Z-Cs-do-Cycloalkyl, Ci-C6-Alkoxy-Ci-C6-alkyl, Ci-C6-Cyanoalkyl, Z-Phenyl, Z-C(=O)-Ra2, Z-SO2R32 und Tri-Ci-C4-alkylsilyl; Ra2 d-Cβ-Alkyl, Ci-C4-Haloalkyl, Z-d-Cβ-Alkoxy, Z-CrC4-HaIo- alkoxy und NR1R";R is hydrogen, Ci -C 6 -alkyl, C 4 haloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 -Alki- nyl, Z-Cs-do-cycloalkyl, Ci-C 6 alkoxy -C-C 6 alkyl, Ci-C 6 cyanoalkyl, phenyl-Z, Z is C (= O) -R a2, Z-SO 2 R 32 and tri-Ci-C4-alkylsilyl; R a2 is C 1 -C 6 -alkyl, C 1 -C 4 -haloalkyl, Zd-C 6 -alkoxy, Z-C 1 -C 4 -haloalkoxy and NR 1 R ";
Z eine kovalente Bindung oder Ci-C4-Alkylen; R1, R" unabhängig voneinander Wasserstoff, CrC8-Alkyl, Ci-C4-Haloalkyl, Cs-Cβ-Alkenyl, C3-C8-Al kinyl, Z-C3-C6-Cycloalkyl, Z-(C=O)-R32, Z-Cr C8-AIkOXy1 Z-CrC8-HaIOaIkOXy;Z is a covalent bond or C 1 -C 4 -alkylene; R 1, R "is independently hydrogen, -C 8 alkyl, Ci-C4-haloalkyl, Cs-Cβ alkenyl, C 3 -C 8 -alkyl kinyl, ZC 3 -C 6 cycloalkyl, Z- (C = O ) -R 32 , Z-Cr C 8 -alkoxy 1 Z-CrC 8 -HaIO-alkoxy;
R1 und R" können auch gemeinsam mit dem N-Atom, an das sie gebunden sind, einen 5- oder θ-gliedrigen monocyclischen oder 9- oder 10-gliedrigen bicyclischer Heterocyclus bilden, enthaltend 1 , 2, 3 oder 4 Heteroatome ausgewählt aus O, N und S; R2 Phenyl, Naphthyl oder und 5- oder 6-gliedriger monocyclischer oder 9- oderR 1 and R "may also together with the N-atom to which they are attached form a 5- or θ-membered monocyclic or 9- or 10-membered bicyclic heterocycle containing 1, 2, 3 or 4 heteroatoms selected from O, N and S; R 2 is phenyl, naphthyl or and 5- or 6-membered monocyclic or 9-or
10-gliedriger bicyclischer aromatischer Heterocyclus, enthaltend 1 , 2, 3 o- der 4 Heteroatome ausgewählt aus O, N und S, wobei die cyclischen Gruppen unsubstituiert oder durch 1 , 2, 3, 4 oder 5 Gruppen Ra substituiert sind, bedeutet; Ra unabhängig voneinander Z-CN, Z-OH, Z-NO2, Z-Halogen, Ci-Cs-Alkyl, CrC4-Haloalkyl, C2-C8-Al kenyl, C2-C8-Al kinyl, Z-d-C8-Alkoxy, Z-CrC8-Haloalkoxy, Z-C3-Cio-Cycloalkyl, 0-Z-C3-Cio-Cycloalkyl, Z-C(=O)-Ra2, NR1R", Z-(Tri-CrC4-alkyl)silyl, Z-Phenyl und S(O)nRbb, wobei Rbb CrC8-Alkyl, CrC6-Haloalkyl und Z-Phenyl bedeutet und n für O, 1 oder 2 steht;A 10-membered bicyclic aromatic heterocycle containing 1, 2, 3 or 4 heteroatoms selected from O, N and S, wherein the cyclic groups are unsubstituted or substituted by 1, 2, 3, 4 or 5 groups R a ; R a independently of one another Z-CN, Z-OH, Z-NO 2 , Z-halogen, C 1 -C 8 -alkyl, C 1 -C 4 -haloalkyl, C 2 -C 8 -alkynyl, C 2 -C 8 -alkynyl, ZDC 8 alkoxy, Z -C 8 haloalkoxy, ZC 3 -Cio cycloalkyl, 0-ZC 3 -Cio cycloalkyl, ZC (= O) -R a2, NR 1 R ", Z (tri-CrC 4 - alkyl) silyl, Z-phenyl and S (O) n R bb , wherein R bb is C 1 -C 8 alkyl, C 1 -C 6 haloalkyl and Z-phenyl, and n is O, 1 or 2;
Ra kann auch gemeinsam mit der an das benachbarte C-Atom gebundene Gruppe Ra einen fünf- oder sechsgliedrigen gesättigten, teilweise oder vollständig ungesättigten Ring bilden, der neben Kohlenstoff- 1 , 2 oder 3 Heteroatome ausgewählt aus O, N und S enthalten kann; X O, S oder N-R;R a can also form, together with the group R a attached to the adjacent carbon atom , a five- or six-membered saturated, partially or completely unsaturated ring which, in addition to carbon atoms, can contain 1, 2 or 3 heteroatoms selected from O, N and S. ; X0, S or NR;
Y R1 oder NH-R; W O oder S; A,E,G,M N und C-Rc, wobei eine oder zwei Gruppen davon N bedeuten, Rc Wasserstoff oder eine der bei Ra genannten Gruppen; wobei in Gruppen R1, R2, R3 und deren Untersubstituenten die Kohlenstoffketten und/oder die cyclischen Gruppen teilweise oder vollständig durch Gruppen Ra substituiert sein können, sowie deren N-Oxide und landwirtschaftlich geeignete Salze.YR 1 or NH-R; WO or S; A, E, G, MN and CR c , where one or two groups thereof are N, R c is hydrogen or one of the groups mentioned in R a ; where in groups R 1 , R 2 , R 3 and their sub-substituents, the carbon chains and / or the cyclic groups may be partially or completely substituted by groups R a , and their N-oxides and agriculturally suitable salts.
2. Verbindungen der Formel I gemäß Anspruch 1 , welche der Formel I' entsprechen2. Compounds of formula I according to claim 1, which correspond to the formula I '
worin die Variablen folgende Bedeutung haben R1 OR oder NR1R"; wherein the variables have the following meaning R 1 OR or NR 1 R ";
R Wasserstoff, Ci -C6-Al kyl, Ci-C4-Haloalkyl, C2-C6-Alkenyl, C3-C6-Alki- nyl, Z-Cs-do-Cycloalkyl, Ci-C6-Alkoxy-Ci-C6-alkyl, Ci-C6-Cyanoalkyl, Z-Phenyl, Z-C(=O)-Ra2 und Tri-Ci-C4-alkylsilyl; Ra2 d-Cβ-Alkyl, Ci-C4-Haloalkyl, Z-Ci-C6-Alkoxy, Z-Ci-C4-HaIo- alkoxy und NR1R";R is hydrogen, Ci -C 6 -alkyl, C 4 haloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 -Alki- nyl, Z-Cs-do-cycloalkyl, Ci-C 6 alkoxy -C 1 -C 6 -alkyl, C 1 -C 6 -cyanoalkyl, Z-phenyl, ZC (= O) -R a 2 and tri-C 1 -C 4 -alkylsilyl; R a2 is C 1 -C 6 -alkyl, C 1 -C 4 -haloalkyl, Z-C 1 -C 6 -alkoxy, Z-C 1 -C 4 -haloalkoxy and NR 1 R ";
Z eine kovalente Bindung oder Ci-C4-Alkylen; R1, R" unabhängig voneinander Wasserstoff, Ci -Ce-Al kyl, Ci-C4-Haloalkyl, Cs-Cs-Alkenyl, C3-C8-Al kinyl, Z-C3-C6-Cycloalkyl, Z-Ci-C8-Alkoxy, Z-Ci-Cs-Haloalkoxy; R1 und R" können auch gemeinsam mit dem N-Atom, an das sie gebunden sind, einen 5- oder θ-gliedrigen monocyclischen oder 9- oder 10-gliedrigen bicyclischer Heterocyclus bilden, enthaltend 1 , 2, 3 oder 4 Heteroatome ausgewählt aus O, N und S;Z is a covalent bond or C 1 -C 4 -alkylene; R 1 , R "independently of one another are hydrogen, C 1 -C 6 -alkyl, C 1 -C 4 -haloalkyl, C 3 -C 8 -alkenyl, C 3 -C 8 -alkynyl, ZC 3 -C 6 -cycloalkyl, Z-Ci- C 8 alkoxy, Z-C 1 -C 8 haloalkoxy, R 1 and R "may also together with the N-atom to which they are attached form a 5- or θ-membered monocyclic or 9- or 10-membered bicyclic heterocycle form containing 1, 2, 3 or 4 heteroatoms selected from O, N and S;
R2 Phenyl oder Naphthyl, wobei die cyclischen Gruppen unsubstituiert oder durch 1 , 2, 3 oder 4 Gruppen Ra substituiert sind, bedeutet;R 2 is phenyl or naphthyl, where the cyclic groups are unsubstituted or substituted by 1, 2, 3 or 4 groups R a ;
Ra unabhängig voneinander Z-CN, Z-OH, Z-NO2, Z-Halogen, Ci-C8-Al- kyl, Ci-C4-Haloalkyl, C2-C8-Al kenyl, C2-C8-Al kinyl, Z-Ci-C8-Alkoxy, Z-Ci-C8-Haloalkoxy, Z-C3-Cio-Cycloalkyl, 0-Z-C3-Cio-Cycloalkyl, Z-C(=O)-Ra2, NR1R", Z-(Tri-Ci-C4-alkyl)silyl, Z-Phenyl und S(O)nRbb, wobei Rbb Ci-C8-Alkyl und Ci-C6-Haloalkyl bedeutet und n für 0, 1 oder 2 steht;R a is independently Z-CN, Z-OH, Z-NO 2, Z is halogen, Ci-C 8 -Al- -alkyl, Ci-C 4 haloalkyl, C 2 -C 8 -alkenyl, C 2 -C 8 -alkynyl, Z-Ci-C 8 -alkoxy, Z-Ci-C 8 -haloalkoxy, ZC 3 -Cio-cycloalkyl, 0-ZC 3 -Cio-cycloalkyl, ZC (= O) -R a2 , NR 1 R ", Z- (tri-C 1 -C 4 -alkyl) silyl, Z-phenyl and S (O) n R bb , wherein R bb is C 1 -C 8 -alkyl and C 1 -C 6 -haloalkyl and n is 0 , 1 or 2 stands;
Ra kann auch gemeinsam mit der an das benachbarte C-Atom gebundene Gruppe Ra einen fünf- oder sechsgliedrigen gesättigten, teilweise oder vollständig ungesättigten Ring bilden, der neben Kohlenstoff- 1 , 2 oder 3 Hete- roatome ausgewählt aus O, N und S enthalten kann;R a can also form, together with the group R a attached to the adjacent carbon atom , a five- or six-membered saturated, partially or completely unsaturated ring which, besides carbon-1, 2 or 3 heteroatoms, is selected from O, N and S. may contain;
X, Y O, S oder N-R;X, Y is O, S or N-R;
A,E,G,M N und C-Rc, wobei eine Gruppe davon N bedeutet, Rc Wasserstoff oder eine der bei Ra genannten Gruppen; wobei in Gruppen R1, R2, R3 und deren Untersubstituenten die Kohlenstoffketten und/oder die cyclischen Gruppen teilweise oder vollständig durch Gruppen Ra substituiert sein können.A, E, G, MN and CR c , a group of which is N, R c is hydrogen or one of the groups mentioned in R a ; where in groups R 1 , R 2 , R 3 and their sub-substituents, the carbon chains and / or the cyclic groups may be partially or completely substituted by groups R a .
3. Verbindungen gemäß Anspruch 1 oder 2, worin Y für OH steht.3. Compounds according to claim 1 or 2, wherein Y is OH.
4. Verbindungen gemäß Anspruch 1 oder 2, worin Y für SH steht.4. Compounds according to claim 1 or 2, wherein Y is SH.
5. Verbindungen gemäß Anspruch 1 oder 2, worin Y für NH-R steht.5. Compounds according to claim 1 or 2, wherein Y is NH-R.
6. Verbindungen gemäß einem der Ansprüche 1 bis 5, worin R1 für CrC4-AIkOXy steht.6. Compounds according to any one of claims 1 to 5, wherein R 1 is C 1 -C 4 -alkoxy.
7. Verbindungen der Formel I gemäß einem der Ansprüche 1 bis 6, welche der Formel 1.1 entsprechen,7. Compounds of the formula I according to any one of claims 1 to 6, which correspond to the formula 1.1,
in der Ra2, Ra3 und Ra4 je einer Gruppe Ra entsprechen. in which R a2 , R a3 and R a4 each correspond to one group R a .
8. Verbindungen der Formel I gemäß einem der Ansprüche 1 bis 7, welche der Formel I.A entsprechen,8. Compounds of formula I according to any one of claims 1 to 7, which correspond to the formula I.A,
in der R5 und R6 für Gruppen Ra und n für eine ganze Zahl von Null bis vier stehen. in which R 5 and R 6 are groups R a and n is an integer from zero to four.
9. Verbindungen der Formel I gemäß einem der Ansprüche 1 bis 8, welche der9. Compounds of formula I according to any one of claims 1 to 8, which of
worin X1 für O oder S steht. wherein X 1 is O or S.
10. Verbindungen der Formel I gemäß einem der vorangegangenen Ansprüche, welche der Formel IT entsprechen, worin Rv für Ci -C8-Al kyl, Ci-C8-Alkylcarbonyl, Ci-C8-Alkylsulfonyl, Ci-C8-Aryl- carbonyl, oder Ci-C8-Arylsulfonyl steht, wobei die Alkyl-, bzw. Arylgruppen teilweise oder vollständig durch Gruppen Ra substituiert sein können.10. Compounds of the formula I according to one of the preceding claims, which correspond to the formula IT, wherein R v is C -C 8 -alkyl, C 8-alkylcarbonyl, Ci-C 8 alkylsulfonyl carbonyl, Ci-C 8 aryl, or C 8 is arylsulfonyl, wherein said alkyl or, Aryl groups may be partially or completely substituted by groups R a .
1 1. Verbindungen der Formel I gemäß einem der vorangegangenen Ansprüche, worin X für O steht.1 1. A compound of formula I according to any one of the preceding claims, wherein X is O.
12. Mittel, enthaltend eine herbizid wirksame Menge mindestens einer Pyridinverbin- düng der Formel I oder eines landwirtschaftlich geeigneten Salzes davon nach einem der Ansprüche 1 bis 1 1 und für die Formulierung von Pflanzenschutzmitteln übliche Hilfsmittel.12. A composition containing a herbicidally effective amount of at least one Pyridinverbin- fertil of the formula I or an agriculturally suitable salt thereof according to any one of claims 1 to 1 1 and for the formulation of pesticides customary auxiliaries.
13. Mittel gemäß Anspruch 12, enthaltend mindestens einen weiteren Wirkstoff.13. Composition according to claim 12, containing at least one further active ingredient.
14. Mittel gemäß Anspruch 12 oder 13, enthaltend zwei weitere Wirkstoffe aus der Gruppe der Herbizide und/oder Safener.14. Composition according to claim 12 or 13, containing two further active compounds from the group of herbicides and / or safeners.
15. Verfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs, dadurch ge- kennzeichnet, dass man eine herbizid wirksame Menge mindestens einer Pyri- dinverbindung der Formel I oder eines landwirtschaftlich brauchbaren Salzes davon nach einem der Ansprüche 1 bis 11 auf Pflanzen, deren Samen und/oder deren Lebensraum einwirken lässt. 15. A method for controlling undesired plant growth, characterized in that a herbicidally effective amount of at least one pyridine compound of the formula I or an agriculturally useful salt thereof according to one of claims 1 to 11 on plants, their seeds and / or their Habitat acts.
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Families Citing this family (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8097712B2 (en) 2007-11-07 2012-01-17 Beelogics Inc. Compositions for conferring tolerance to viral disease in social insects, and the use thereof
US8962584B2 (en) 2009-10-14 2015-02-24 Yissum Research Development Company Of The Hebrew University Of Jerusalem, Ltd. Compositions for controlling Varroa mites in bees
WO2011064188A1 (en) 2009-11-27 2011-06-03 Basf Se Insecticidal methods using nitrogen-containing heteroaromatic compounds
CN102822350B (en) 2010-03-08 2015-05-06 孟山都技术公司 Polynucleotide molecules for gene regulation in plants
EA201201322A1 (en) 2010-03-23 2013-05-30 Басф Се Pyridine, possessing herbicidal action
AR081526A1 (en) 2010-03-23 2012-10-03 Basf Se PIRIDAZINAS REPLACED THAT HAVE HERBICITY ACTION
CN102822179A (en) 2010-03-23 2012-12-12 巴斯夫欧洲公司 Pyrazinothiazines having herbicidal action
JP2013522339A (en) 2010-03-23 2013-06-13 ビーエーエスエフ ソシエタス・ヨーロピア Substituted pyridines with herbicidal action
WO2013039990A1 (en) 2011-09-13 2013-03-21 Monsanto Technology Llc Methods and compositions for weed control
AU2012308686B2 (en) 2011-09-13 2018-05-10 Monsanto Technology Llc Methods and compositions for weed control
US10760086B2 (en) 2011-09-13 2020-09-01 Monsanto Technology Llc Methods and compositions for weed control
EP2756084B1 (en) 2011-09-13 2020-06-03 Monsanto Technology LLC Methods and compositions for weed control
WO2013040033A1 (en) 2011-09-13 2013-03-21 Monsanto Technology Llc Methods and compositions for weed control
BR112014005795A2 (en) 2011-09-13 2020-12-08 Monsanto Technology Llc methods of controlling plants, reducing the expression of a plant's hppd gene, preparing a nucleotide, and identifying polynucleotides useful in modulating the expression of the hppd gene in the external treatment of a plant, compositions and cassette of microbial expression
EP2755988B1 (en) 2011-09-13 2018-08-22 Monsanto Technology LLC Methods and compositions for weed control
AU2012308660B2 (en) 2011-09-13 2017-05-25 Monsanto Technology Llc Methods and compositions for weed control
US10829828B2 (en) 2011-09-13 2020-11-10 Monsanto Technology Llc Methods and compositions for weed control
US10806146B2 (en) 2011-09-13 2020-10-20 Monsanto Technology Llc Methods and compositions for weed control
CA2848689A1 (en) 2011-09-13 2013-03-21 Monsanto Technology Llc Methods and compositions for weed control targeting pds
US10240161B2 (en) 2012-05-24 2019-03-26 A.B. Seeds Ltd. Compositions and methods for silencing gene expression
CA2896762A1 (en) 2013-01-01 2014-07-10 A.B. Seeds Ltd. Methods of introducing dsrna to plant seeds for modulating gene expression
US10683505B2 (en) 2013-01-01 2020-06-16 Monsanto Technology Llc Methods of introducing dsRNA to plant seeds for modulating gene expression
AU2014249015B2 (en) 2013-03-13 2020-04-16 Monsanto Technology Llc Methods and compositions for weed control
CA2905104A1 (en) 2013-03-13 2014-10-09 Monsanto Technology Llc Control of lolium species by topical application of herbicidal composition comprising dsrna
US10568328B2 (en) 2013-03-15 2020-02-25 Monsanto Technology Llc Methods and compositions for weed control
PL3030663T3 (en) 2013-07-19 2020-04-30 Monsanto Technology Llc Compositions and methods for controlling leptinotarsa
US9850496B2 (en) 2013-07-19 2017-12-26 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
PL3066200T3 (en) 2013-11-04 2025-03-31 Greenlight Biosciences, Inc. Compositions and methods for controlling arthropod parasite and pest infestations
UA119253C2 (en) 2013-12-10 2019-05-27 Біолоджикс, Інк. METHOD FOR VARROA TREATMENT AND VEGETABLES
AR099092A1 (en) 2014-01-15 2016-06-29 Monsanto Technology Llc METHODS AND COMPOSITIONS FOR WEED CONTROL USING EPSPS POLYUCLEOTIDES
EP3420809A1 (en) 2014-04-01 2019-01-02 Monsanto Technology LLC Compositions and methods for controlling insect pests
EA031500B1 (en) 2014-04-10 2019-01-31 Басф Се HERBICIDAL COMPOSITION COMPRISING ISOXAZOLO[5,4-b]PYRIDINE
CN106795515B (en) 2014-06-23 2021-06-08 孟山都技术公司 Compositions and methods for regulating gene expression via RNA interference
EP3161138A4 (en) 2014-06-25 2017-12-06 Monsanto Technology LLC Methods and compositions for delivering nucleic acids to plant cells and regulating gene expression
AR101348A1 (en) 2014-07-29 2016-12-14 Monsanto Technology Llc COMPOSITIONS AND METHODS FOR PEST CONTROL BY INSECTS
UA124255C2 (en) 2015-01-22 2021-08-18 Монсанто Текнолоджі Елелсі INSECTICIDAL COMPOSITION AND METHOD OF CONTROL OF LEPTINOTARSA
UY36703A (en) 2015-06-02 2016-12-30 Monsanto Technology Llc COMPOSITIONS AND METHODS FOR THE ADMINISTRATION OF A POLINUCLEOTIDE ON A PLANT
WO2016196782A1 (en) 2015-06-03 2016-12-08 Monsanto Technology Llc Methods and compositions for introducing nucleic acids into plants

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AR023071A1 (en) * 1998-12-23 2002-09-04 Syngenta Participations Ag PIRIDINCETONE COMPOUNDS, INTERMEDIATE COMPOUNDS, HERBICITY AND INHIBITOR COMPOSITION OF PLANTAGE GROWTH, METHOD FOR CONTROLLING INDESATED VEGETATION, METHOD FOR INHIBITING GROWTH OF PLANTS, AND USE OF COMPOSITION TO GROW GROWTH.
DE10125432A1 (en) * 2001-05-25 2002-11-28 Bayer Ag New benzoyl-substituted aliphatic ketones or aldehydes, useful as herbicides or fungicides, especially as pre- and post-emergence selective herbicides against a broad spectrum of weeds
DE102006043443A1 (en) * 2006-09-15 2008-03-27 Bayer Healthcare Ag Novel aza-bicyclic compounds and their use

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010069802A1 *

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