WO2004067518A1 - Substituted pyrimidines - Google Patents

Substituted pyrimidines Download PDF

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Publication number
WO2004067518A1
WO2004067518A1 PCT/EP2004/000345 EP2004000345W WO2004067518A1 WO 2004067518 A1 WO2004067518 A1 WO 2004067518A1 EP 2004000345 W EP2004000345 W EP 2004000345W WO 2004067518 A1 WO2004067518 A1 WO 2004067518A1
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WIPO (PCT)
Prior art keywords
halogen
optionally substituted
cyano
alkyl
methyl
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Application number
PCT/EP2004/000345
Other languages
German (de)
French (fr)
Inventor
Ernst Rudolf Gesing
Mark Wilhelm Drewes
Peter Dahmen
Dieter Feucht
Rolf Pontzen
Original Assignee
Bayer Cropscience Aktiengesellschaft
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Publication of WO2004067518A1 publication Critical patent/WO2004067518A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/60—Three or more oxygen or sulfur atoms

Definitions

  • the invention relates to new substituted pyrimidines, processes for their preparation and their use as plant treatment agents, in particular as herbicides.
  • n stands for the numbers 0, 1 or 2
  • Q represents O (oxygen) or S (sulfur),
  • R 1 represents hydrogen, halogen or optionally substituted in each case
  • R 2 stands for hydrogen, for halogen, or for optionally substituted alkyl, alkoxy, alkylthio, alkylarnino or dialkyla ino
  • R 3 represents hydrogen or represents optionally substituted alkyl or cycloalkyl
  • R 4 represents hydrogen or represents optionally substituted alkyl or phenyl
  • X stands for cyano, nitro, halogen or for each optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, or two adjacent groups X also stand together for a benzo group
  • Saturated or unsaturated hydrocarbon groups such as alkyl, alkanediyl, alkenyl or alkynyl, are in each case straight-chain or branched as far as possible, even in linkages with heteroatoms, such as in alkoxy.
  • Optionally substituted radicals can be mono- or polysubstituted, whereby in the case of multiple substitution the substituents can be the same or different.
  • the compounds of the general formula (I) according to the invention optionally contain one or more asymmetrically substituted carbon atoms and in these cases can be present in various enantiomeric (R- and S-configured forms) or diastereomeric forms.
  • the invention relates both to the use of the various possible individual enantiomeric or stereoisomeric forms of the compounds of the general formula (T) and to the mixtures of these isomeric compounds.
  • R 1 preferably represents hydrogen, halogen, alkyl or alkoxy each optionally substituted by halogen or d-Gi-alkoxy, each having 1 to 6 carbon atoms in the alkyl groups, or alkylthio, alkylarnino or dialkylamino, each having 1 to 6 carbon atoms in the alkyl groups.
  • R 2 preferably represents hydrogen, halogen, alkyl or alkoxy each optionally substituted by halogen or C 1 -C 4 -alkoxy, each having 1 to 6 carbon atoms in the alkyl groups, or alkylthio, alkylamino or dialkylamino each having 1 to 6 Carbon atoms in the
  • R 3 preferably represents hydrogen, alkyl having 1 to 6 carbon atoms optionally substituted by cyano, halogen or -Gralkoxy, or optionally substituted by cyano, halogen or - - alkyl
  • R 4 preferably represents hydrogen, alkyl having 1 to 6 carbon atoms optionally substituted by cyano, halogen or Ci-C 4 alkoxy, or optionally nitro, cyano, halogen, C 1 -C 4 alkyl, Ci-C 4 -Halogenoalkyl, C 1 -C -alkoxy or C 1 -C -haloalkoxy substituted phenyl.
  • X preferably stands for cyano, nitro, halogen or for alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl with 1 to 6 carbon atoms, which are optionally substituted by halogen, or two adjacent groups X also together for a benzo group.
  • R 1 particularly preferably represents hydrogen, fluorine, chlorine, bromine, iodine, and in each case methyl, ethyl, n- or i-propyl, methoxy optionally substituted by fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy , Ethoxy, n- or , "_ ⁇ O 004/067518
  • i-propoxy for methylthio, ethylthio, n- or i-propylthio, methylamino, emylamino, n- or i-propylarnino, dimemylamino or diethylamino.
  • R 2 particularly preferably stands for hydrogen, for fluorine, chlorine, bromine, iodine, for methyl, ethyl, n- or i-propyl, methoxy which are each optionally substituted by fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy , Ethoxy, n- or i-propoxy, for methylthio, ethylthio, n- or i-propylthio, methylamino,
  • R 3 particularly preferably represents hydrogen, in each case optionally by
  • R 4 particularly preferably represents hydrogen, in each case methyl, ethyl, n- or i-propyl optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, or optionally by nitro, cyano, fluorine, Chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or
  • X particularly preferably represents cyano, nitro, fluorine, chlorine, bromine, iodine, or methyl, ethyl, n- or i-propyl, n-, i-, s- or t- which is optionally substituted by fluorine and / or chlorine. Butyl, methoxy, ethoxy, n- or i-
  • R very particularly preferably represents chlorine, methyl, ethyl, methoxy or ethoxy optionally substituted by fluorine, chlorine, methoxy or ethoxy, methylthio, ethylthio, methylamine, ethylamino or dimethylamino.
  • R very particularly preferably represents chlorine, in each case methyl, ethyl, methoxy or ethoxy which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, represents methylthio, ethylthio, methylamino, ethylamino or dimethylamino.
  • R very particularly preferably represents hydrogen, each methyl or ethyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, or cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl optionally substituted by fluorine, chlorine or methyl.
  • R 4 very particularly preferably represents hydrogen, in each case methyl or ethyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, or phenyl.
  • X very particularly preferably represents cyano, nitro, fluorine, chlorine, bromine, iodine, or methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy which is optionally substituted by fluorine and / or chlorine , Methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, emylsulfinyl, methylsulfonyl or ethylsulfonyl, or two adjacent groups X also together for a benzo group.
  • a very particularly preferred group are also those compounds in which Q is O (oxygen), R 1 and R 2 are methoxy and R 3 , R 4 and X have the meaning particularly preferred above.
  • R 1 and R 2 are most preferably methoxy.
  • R 3 most preferably represents hydrogen.
  • R 4 most preferably represents hydrogen, in each case methyl or ethyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy.
  • X most preferably represents fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, or two adjacent groups X together also for a benzo group.
  • the new substituted pyrimidines of the general formula (T) are notable for strong and selective herbicidal activity.
  • R and R have the meaning given above and.
  • Y represents halogen, alkylthio, alkylsulfonyl or alkylsulfonyl
  • Y preferably represents fluorine, chlorine, bromine, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, in particular methylsulfonyl.
  • the starting materials of the general formula (H) are known and / or can be prepared by processes known per se (cf. J. Chem. Soc. 1957, 1830; J ..
  • Formula (TU) provides a general definition of the nucleophilic compounds to be used as starting materials in the process according to the invention for the preparation of compounds of the general formula (I).
  • general formula (I) provides a general definition of the nucleophilic compounds to be used as starting materials in the process according to the invention for the preparation of compounds of the general formula (I).
  • R 3 has the meaning given above and
  • R represents alkyl, in particular methyl or ethyl
  • a diluent e.g. Water
  • a diluent e.g. Water
  • arylalkylamines of the formula (TV) required as precursors are known and / or can be prepared by processes known per se (cf. J. Am. Chem. Soc. 76/1954, 5589-5597; Synthetic Commun. 7 (1977), 71-78; manufacturing examples).
  • N-cyano-imidates of the formula (V) required as precursors are known organic synthetic chemicals.
  • reaction auxiliaries The usual inorganic or organic bases or acid acceptors are generally suitable as reaction aids for the process according to the invention. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkanolates, such as sodium, potassium or calcium acetate, lithium, sodium, potassium or calcium amide, sodium, potassium, cesium or calcium carbonate, sodium, potassium or calcium hydrogen carbonate, lithium, sodium, potassium or calcium hydride, lithium, sodium, potassium or calcium hydroxide, sodium or potassium methoxide, ethanolate, -n- or -i-propanolate, -n -
  • DABCO 1,4-diazabicyclo [2,2,2] octane
  • DBN 1,5-diazabicyclo [ 4,3,0] -non-5-ene
  • DBU 1,8-diazabicyclo [5,4,0] -undec-7-ene
  • Formula (I) is preferably carried out using one or more diluents.
  • Inert organic solvents are particularly suitable as diluents for carrying out the process according to the invention. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene,
  • Xylene chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or emylene glycol dimethyl or diethyl ether; Ketones such as acetone, butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or butyronitrile; Amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-
  • the reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 120 ° C.
  • the process according to the invention is generally carried out under normal pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressure - generally between 0.1 bar and 10 bar.
  • the starting materials are generally used in approximately equimolar amounts. However, it is also possible to use one of the components in a larger excess.
  • the reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary and the reaction mixture is generally stirred at the required temperature for several hours. Working up is carried out according to customary methods (cf. the production examples).
  • the active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers. Weeds in the broadest sense are understood to mean all plants that grow up in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
  • the active compounds according to the invention can e.g. can be used in the following plants:
  • the active compounds according to the invention are suitable for combating total weeds, e.g. on industrial and track systems and on
  • the active compounds according to the invention for combating herbaceous weed in Da ⁇ erkulturen for example forest, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants , on ornamental and sports turf and pasture land as well as for selective weed control in annual crops.
  • the compounds of formula (I) according to the invention show strong herbicidal activity and a broad spectrum of activity when used on the soil and on above-ground parts of plants. To a certain extent, they are also suitable for the selective control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops, both in the pre-emergence and in the post-emergence process.
  • the active compounds according to the invention can also be used to control animal pests and fungal or bacterial plant diseases. If appropriate, they can also be used as intermediates or precursors for the synthesis of further active compounds.
  • plants and parts of plants can be treated.
  • Plants are understood here to mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
  • Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant cultivars which can or cannot be protected by plant breeders' rights.
  • Plant parts are to be understood to mean all above-ground and underground parts and organs of plants, such as shoots, leaves, flowers and roots, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes.
  • the plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.
  • the treatment of the plants and parts of plants with the active compounds according to the invention is carried out directly or by acting on their surroundings, living space or storage space using the customary treatment methods, for example by dipping, spraying, Evaporation, nebulization, scattering, spreading and, in the case of propagation material, in particular seeds, also by means of single- or multi-layer coating.
  • the active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances and very fine encapsulations in polymers substances.
  • formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, that is liquid solvents and / or the solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can also be used as auxiliary solvents.
  • auxiliary solvents e.g. organic solvents
  • aromatics such as xylene, toluene, or alkylnaphthalenes
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
  • aliphatic hydrocarbons such as cyclohexane or paraffins, e.g.
  • Petroleum fractions mineral and vegetable oils, alcohols such as butanol or glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • Possible solid carriers are: e.g. Ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite,
  • Possible emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; The following may be used as dispersants: for example lignin sulfite waste liquor and methyl cellulose.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins and synthetic phospholipids, can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
  • the formulations generally contain between 0.1 and 95 percent by weight
  • Active ingredient preferably between 0.5 and 90%.
  • the active compounds according to the invention can also be used in a mixture with known herbicides and / or with substances which improve crop tolerance (“safeners”) for weed control, finished formulations or tank mixes being possible mixtures with weed control compositions which contain one or more known herbicides and a safener are also possible.
  • safeners substances which improve crop tolerance
  • herbicides are suitable for the mixtures, for example Acetochlor, Acifluorfen (-sodium), Aclonifen, Alachlor, Alloxydim (-sodium), Ametryne, Amicarbazone, Amidochlor, Amidosulfuron, Anilofos, Asulam, Atrazine, Azafenidin, Azimsulfuron, Beflubutamide, Benazolin (-ethyl), Benulfureson -methyl), bentazone, benzfendizone, benzobicyclone, benzofenap, benzoylprop (-ethyl), bialaphos, bifenox, bispyribac (-sodium), bromobutide, bromofenoxime,
  • Metolachlor Metosulam, Metoxuron, Metribuzin, Metsulfuron (-methyl), Molinate, Monolinuron, naproanilide, napropa ide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pendralin, pentoxamidafen, pentoxamidafen, pentoxamidon, pentoxamidon, pentoxamidon, poxy , Pretilachlor, Primisulfuron (-methyl), Profluazol, Profoxydim, Prometryn, Propachlor, Propanil, Propaquizafop, Propisochlor, Propoxycarbazone (-sodium), Propyzamide, Pro
  • Known safeners are also suitable for the mixtures, for example AD-67, BAS-145138, Benoxacor, Cloquintocet (-mexyl), Cyometrinil, 2,4-D, DKA-24, dichlormid, Dymron, Fenclorim, Fenchlorazole (-ethyl) , Flurazole, fluxofenim, furilazole, isoxadifen (-ethyl), MCPA, mecoprop (-P), mefenpyr (-diethyl), MG-
  • a mixture with other known active compounds such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.
  • the active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying,
  • the active compounds according to the invention can be applied both before and after emergence of the plants. They can also be worked into the soil before sowing.
  • the amount of active ingredient used can vary over a wide range. It essentially depends on the type of effect desired. In general, the application rates are between 1 g and 10 kg of active ingredient per hectare of soil, preferably between 5 g and 5 kg per ha.
  • plants and their parts can be treated.
  • plant species and plant cultivars which occur wildly or are obtained by conventional organic breeding methods, such as crossing or protoplast fusion, and parts thereof are treated.
  • transgenic plants and plant cultivars which have been obtained by genetic engineering methods, optionally in combination with conventional methods (genetically modified organisms) and their parts are treated.
  • the term "parts” or "parts of plants” or “plant parts” was explained above.
  • Plants of the plant varieties which are in each case commercially available or in use are particularly preferably treated according to the invention.
  • Plant cultivars are understood to mean plants with certain properties (“traits”) which have been obtained by conventional breeding, by mutagenesis, or else by recombinant DNA techniques. These can be varieties, bio and genotypes.
  • the treatment according to the invention can also cause superadditive (“synergistic") effects.
  • superadditive for example, reduced application rates and / or widening of the spectrum of activity and / or an increase in the effect of the reversible substances and agents - also in combination with other agrochemical active ingredients, better growth of crop plants, increased tolerance of crop plants to high or low temperatures, increased tolerance of crop plants to dryness or to water or soil salt content, increased flowering performance, easier harvesting, acceleration the ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or processability of the harvested products, which go beyond the effects that are actually to be expected.
  • the preferred transgenic (genetically engineered) plants or plant cultivars to be treated according to the invention include all plants which, by virtue of the genetic engineering modification, have received genetic material which gives these plants particularly advantageous properties (“traits”). Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to
  • Pests such as insects, mites, phytopathogenic fungi, bacteria and / or viruses, and an increased tolerance of the plants to certain herbicidal active ingredients.
  • transgenic plants include the important crop plants, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, rapeseed and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with corn, soybeans, potatoes , Cotton and rapeseed are highlighted.
  • the traits are particularly emphasized as the increased defense of the plants against insects by toxins which arise in the plants, in particular those which are caused by the genetic material from Bacillus thuringiensis (for example by the genes Cry ⁇ A (a), CryIA (b), Cry ⁇ A (c), CryUA, CrylUA, CryIlTß2, Cry9c Cry2Ab,
  • Cry3Bb and CrylF and their combinations are generated in the plants (in following "Bt plants”).
  • the increased defense of plants against are also particularly emphasized as traits. Fungi, bacteria and viruses through systemic acquired resistance (SAR), systemin, phytoalexins, elicitors as well as resistance genes and correspondingly expressed proteins and toxins.
  • SAR systemic acquired resistance
  • the increased tolerance of the plants to certain herbicidal active compounds for example imidazolinones, sulfonylureas, glyphosate or phosphinothricin (for example “PAT” gene), is also particularly emphasized as characteristic traits.
  • the genes conferring the desired properties (“traits”) can also occur in combinations with one another in the transgenic plants.
  • Bt plants are maize varieties, cotton varieties, soy varieties and potato varieties that are sold under the trade names YLELD GARD® (e.g. corn, cotton, soy), KnockOut® (e.g. corn), StarLink® (e.g. corn), Bollgard® ( Cotton), Nucotn® (cotton) and NewLeaf® (potato).
  • herbicide-tolerant plants are corn varieties, cotton varieties and soy varieties that are sold under the trade names Roundup Ready® (tolerance to glyphosate e.g. corn, cotton, soy), Liberty Link® (tolerance to phosphinothricin, e.g.
  • rapeseed rapeseed
  • EVA® tolerance against imidazolinones
  • STS® tolerance to sulfonylureas such as corn.
  • herbicide-resistant plants are the varieties sold under the name Clearfield® (for example maize). Of course, these statements also apply to plant varieties developed in the future or coming onto the market in the future with these or future-developed genetic properties ("traits").
  • the plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula I or the active compound mixtures according to the invention, the synergistic effects mentioned above occurring with the transgenic plants or plant cultivars in addition to the good control of the weed plants.
  • the preferred ranges given above for the active ingredients or mixtures also apply to the treatment of these plants.
  • Especially plant treatment with the compounds or mixtures specifically listed in the present text should be emphasized.
  • the calibration was carried out using unbranched alkan-2-ones (with 3 to 16 carbon atoms) whose logP values are known (determination of the logP values using the
  • the lambda max values were determined on the basis of the UV spectra from 200 nm to 400 nm in the maxima of the chromatographic signals.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
  • Seeds of the test plants are sown in normal soil. After 24 hours, the soil is sprayed with the active ingredient preparation in such a way that the desired amount of active ingredient is applied per unit area.
  • the active ingredient concentration in the spray liquor is chosen so that the desired amount of active ingredient is applied in 1000 liters of water per hectare.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • Test plants with a height of 5 - 15 cm are sprayed with the active ingredient preparation in such a way that the desired quantities of active substances are applied per unit area.
  • the concentration of the spray liquor is chosen so that in
  • the degree of damage to the plants is rated in% damage compared to the development of the untreated control.
  • the compounds according to Preparation Examples 2, 5, 10 and 12 show some of which are well tolerated by crop plants, such as e.g. Corn and sugar beet, strong weed control.

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

Abstract

The invention relates to novel substituted pyrimidines of formula (I), in which R1, R2, R3, R4, Q, X and n have the meanings as cited in the description. The invention also relates to a method and intermediate products for producing these pyrimidines, and to the use thereof as plant control agents, particularly as herbicides.

Description

Substituierte PyrimidineSubstituted pyrimidines
Die Erfindung betrifft neue substituierte Pyrimidine, Verfahren zu ihrer Herstellung und ihre Verwendung als Pflanzenbehandlungsmittel, insbesondere als Herbizide.The invention relates to new substituted pyrimidines, processes for their preparation and their use as plant treatment agents, in particular as herbicides.
Es ist bereits bekannt, dass bestimmte substituierte Pyrimidine herbizide Eigenschaften aufweisen (vgl. EP-A 0 249 708, EP-A 0 287 079, WO-02/34724). Die Wirkung dieser Verbindungen ist jedoch nicht in allen Belangen zufriedenstellend.It is already known that certain substituted pyrimidines have herbicidal properties (cf. EP-A 0 249 708, EP-A 0 287 079, WO-02/34724). However, the action of these compounds is not satisfactory in all respects.
Es wurden nun die neuen substituierten Pyrimidine der allgemeinen Formel (I)The new substituted pyrimidines of the general formula (I)
Figure imgf000003_0001
in welcher
Figure imgf000003_0001
in which
n für die Zahlen 0, 1 oder 2 stehtn stands for the numbers 0, 1 or 2
Q für O (Sauerstoff) oder S (Schwefel) steht,Q represents O (oxygen) or S (sulfur),
R1 für Wasserstoff, für Halogen, oder für jeweils gegebenenfalls substituiertesR 1 represents hydrogen, halogen or optionally substituted in each case
Alkyl, Alkoxy, Alkylthio, Alkylarnino oder Dialkylamino steht,Alkyl, alkoxy, alkylthio, alkylarnino or dialkylamino,
R2 für Wasserstoff, für Halogen, oder für jeweils gegebenenfalls substituiertes Alkyl, Alkoxy, Alkylthio, Alkylarnino oder Dialkyla ino steht, R3 für Wasserstoff oder für jeweils gegebenenfalls substituiertes Alkyl oder Cycloalkyl steht,R 2 stands for hydrogen, for halogen, or for optionally substituted alkyl, alkoxy, alkylthio, alkylarnino or dialkyla ino, R 3 represents hydrogen or represents optionally substituted alkyl or cycloalkyl,
R4 für Wasserstoff oder für jeweils gegebenenfalls substituiertes Alkyl oder Phenyl steht, undR 4 represents hydrogen or represents optionally substituted alkyl or phenyl, and
X für Cyano, Nitro, Halogen oder für jeweils gegebenenfalls substituiertes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl steht, oder zwei benachbarte Gruppierungen X auch zusammen für eine Benzo-Gruppierung stehenX stands for cyano, nitro, halogen or for each optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, or two adjacent groups X also stand together for a benzo group
gefunden.found.
Gesättigte oder ungesättigte Kohlenwasserstoffgruppierungen, wie Alkyl, Alkandiyl, Alkenyl oder Alkinyl, sind - auch in Verknüpfungen mit Heteroatomen, wie in Al- koxy - soweit möglich j eweils geradkettig oder verzweigt.Saturated or unsaturated hydrocarbon groups, such as alkyl, alkanediyl, alkenyl or alkynyl, are in each case straight-chain or branched as far as possible, even in linkages with heteroatoms, such as in alkoxy.
Gegebenenfalls substituierte Reste können einfach oder mehrfach substituiert sein, wobei bei Mehrfachsubstitution die Substituenten gleich oder verschieden sein können.Optionally substituted radicals can be mono- or polysubstituted, whereby in the case of multiple substitution the substituents can be the same or different.
Die erfindungsgemäßen Verbindungen der allgemeinen Formel (I) enthalten gegebenenfalls ein oder mehrere asymmetrisch substituierte Kohlenstoffatome und kön- nen in diesen Fällen in verschiedenen enantiomeren (R- und S- konfigurierten Formen) bzw. diastereomeren Formen vorliegen. Die Erfindung betrifft in diesen Fällen sowohl die Verwendung der verschiedenen möglichen einzelnen enantiomeren bzw. stereoisomeren Formen der Verbindungen der allgemeinen Formel (T) wie auch der Gemische dieser isomeren Verbindungen.The compounds of the general formula (I) according to the invention optionally contain one or more asymmetrically substituted carbon atoms and in these cases can be present in various enantiomeric (R- and S-configured forms) or diastereomeric forms. In these cases, the invention relates both to the use of the various possible individual enantiomeric or stereoisomeric forms of the compounds of the general formula (T) and to the mixtures of these isomeric compounds.
Bevorzugte Substituenten bzw. Bereiche der in den oben und nachstehend aufge- führten Formeln vorhandenen Reste werden im folgenden definiert. 004/067518Preferred substituents or ranges of the radicals present in the formulas listed above and below are defined below. 004/067518
R1 steht bevorzugt für Wasserstoff, für Halogen, für jeweils gegebenenfalls durch Halogen oder d-Gi-Alkoxy substituiertes Alkyl oder Alkoxy mit jeweils 1 bis 6 Kohlenstoffatomen in den Alkylgruppen, oder für Alkylthio, Alkylarnino oder Dialkylamino mit jeweils 1 bis 6 Kohlenstoffatomen in den Alkylgruppen.R 1 preferably represents hydrogen, halogen, alkyl or alkoxy each optionally substituted by halogen or d-Gi-alkoxy, each having 1 to 6 carbon atoms in the alkyl groups, or alkylthio, alkylarnino or dialkylamino, each having 1 to 6 carbon atoms in the alkyl groups.
R2 steht bevorzugt für Wasserstoff, für Halogen, für jeweils gegebenenfalls durch Halogen oder Cι-C4-Alkoxy substituiertes Alkyl oder Alkoxy mit jeweils 1 bis 6 Kohlenstoffatomen in den Alkylgruppen, oder für Alkylthio, Al- kylamino oder Dialkylamino mit jeweils 1 bis 6 Kohlenstoffatomen in denR 2 preferably represents hydrogen, halogen, alkyl or alkoxy each optionally substituted by halogen or C 1 -C 4 -alkoxy, each having 1 to 6 carbon atoms in the alkyl groups, or alkylthio, alkylamino or dialkylamino each having 1 to 6 Carbon atoms in the
Alkylgruppen.Alkyl groups.
R3 steht bevorzugt für Wasserstoff, für gegebenenfalls durch Cyano, Halogen oder -GrAlkoxy substituiertes Alkyl mit 1 bis 6 Kohlenstoffatomen, oder für gegebenenfalls durch Cyano, Halogen oder - - Alkyl substituiertesR 3 preferably represents hydrogen, alkyl having 1 to 6 carbon atoms optionally substituted by cyano, halogen or -Gralkoxy, or optionally substituted by cyano, halogen or - - alkyl
Cycloalkyl mit 3 bis 6 Kohlenstoffatomen.Cycloalkyl of 3 to 6 carbon atoms.
R4 steht bevorzugt für Wasserstoff, für gegebenenfalls durch Cyano, Halogen oder Ci-C4-Alkoxy substituiertes Alkyl mit 1 bis 6 Kohlenstoffatomen, oder für gegebenenfalls durch Nitro, Cyano, Halogen, C1-C4-Alkyl, Ci-C4-Halo- genalkyl, C1-C -Alkoxy oder C1-C -Halogenalkoxy substituiertes Phenyl.R 4 preferably represents hydrogen, alkyl having 1 to 6 carbon atoms optionally substituted by cyano, halogen or Ci-C 4 alkoxy, or optionally nitro, cyano, halogen, C 1 -C 4 alkyl, Ci-C 4 -Halogenoalkyl, C 1 -C -alkoxy or C 1 -C -haloalkoxy substituted phenyl.
X steht bevorzugt für Cyano, Nitro, Halogen oder für jeweils gegebenenfalls durch Halogen substituiertes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl oder Alkylsulfonyl mit 1 bis 6 Kohlenstoffatomen, oder zwei benachbarte Gruppierungen X auch zusammen für eine Benzo-Gruppierung.X preferably stands for cyano, nitro, halogen or for alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl with 1 to 6 carbon atoms, which are optionally substituted by halogen, or two adjacent groups X also together for a benzo group.
R1 steht besonders bevorzugt für Wasserstoff, für Fluor, Chlor, Brom, Iod, für jeweils gegebenenfalls durch Fluor, Chlor, Methoxy, Ethoxy, n- oder i-Pro- poxy substituiertes Methyl, Ethyl, n- oder i-Propyl, Methoxy, Ethoxy, n- oder , „_Λ O 004/067518R 1 particularly preferably represents hydrogen, fluorine, chlorine, bromine, iodine, and in each case methyl, ethyl, n- or i-propyl, methoxy optionally substituted by fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy , Ethoxy, n- or , "_ Λ O 004/067518
i-Propoxy, für Methylthio, Ethylthio, n- oder i-Propylthio, Methylamino, Emylamino, n- oder i-Propylarnino, Dimemylamino oder Diethylamino.i-propoxy, for methylthio, ethylthio, n- or i-propylthio, methylamino, emylamino, n- or i-propylarnino, dimemylamino or diethylamino.
R2 steht besonders bevorzugt für Wasserstoff, für Fluor, Chlor, Brom, lod, für jeweils gegebenenfalls durch Fluor, Chlor, Methoxy, Ethoxy, n- oder i-Pro- poxy substituiertes Methyl, Ethyl, n- oder i-Propyl, Methoxy, Ethoxy, n- oder i-Propoxy, für Methylthio, Ethylthio, n- oder i-Propylthio, Methylamino,R 2 particularly preferably stands for hydrogen, for fluorine, chlorine, bromine, iodine, for methyl, ethyl, n- or i-propyl, methoxy which are each optionally substituted by fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy , Ethoxy, n- or i-propoxy, for methylthio, ethylthio, n- or i-propylthio, methylamino,
Ethylamino, n- oder i-Propylamino, Dimemylamino oder Diemylamino.Ethylamino, n- or i-propylamino, dimemylamino or diemylamino.
R3 steht besonders bevorzugt für Wasserstoff, für jeweils gegebenenfalls durchR 3 particularly preferably represents hydrogen, in each case optionally by
Cyano, Fluor, Chlor, Methoxy, Ethoxy, n- oder i-Propoxy substituiertes Methyl, Ethyl, n- oder i-Propyl, oder für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methyl, Ethyl, n- oder i-Propyl substituiertes Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl.Cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy substituted methyl, ethyl, n- or i-propyl, or for each optionally substituted by cyano, fluorine, chlorine, methyl, ethyl, n- or i-propyl Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
R4 steht besonders bevorzugt für Wasserstoff, für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy, Ethoxy, n- oder i-Propoxy substituiertes Methyl, Ethyl, n- oder i-Propyl, oder für gegebenenfalls durch Nitro, Cyano, Fluor, Chlor, Brom, Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- öder t-Butyl, Trifluormethyl, Methoxy, Ethoxy, n- oder i-Propoxy, Difluormethoxy oderR 4 particularly preferably represents hydrogen, in each case methyl, ethyl, n- or i-propyl optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, or optionally by nitro, cyano, fluorine, Chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or
Trifluormethoxy substituiertes Phenyl.Trifluoromethoxy substituted phenyl.
X steht besonders bevorzugt für Cyano, Nitro, Fluor, Chlor, Brom, lod, oder für jeweils gegebenenfalls durch Fluor und/oder Chlor substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Methoxy, Ethoxy, n- oder i-X particularly preferably represents cyano, nitro, fluorine, chlorine, bromine, iodine, or methyl, ethyl, n- or i-propyl, n-, i-, s- or t- which is optionally substituted by fluorine and / or chlorine. Butyl, methoxy, ethoxy, n- or i-
Propoxy, n-, i-, s- oder t-Butoxy, Methylthio, Ethylthio, n- oder i-Propylthio, Methylsulfinyl, Ethylsulfinyl, n- oder i-Propylsulfinyi, Methylsulfonyl oder Ethylsulfonyl, oder zwei benachbarte Gruppierungen X auch zusammen für eine Benzo-Gruppierung. 004/067518Propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyi, methylsulfonyl or ethylsulfonyl, or two adjacent groups X together for one benzo grouping. 004/067518
R steht ganz besonders bevorzugt für Chlor, für jeweils gegebenenfalls durch Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl, Ethyl, Methoxy oder Ethoxy, für Methylthio, Ethylthio, Me yla ino, Ethylamino oder Di- memylamino.R very particularly preferably represents chlorine, methyl, ethyl, methoxy or ethoxy optionally substituted by fluorine, chlorine, methoxy or ethoxy, methylthio, ethylthio, methylamine, ethylamino or dimethylamino.
R steht ganz besonders bevorzugt für Chlor, für jeweils gegebenenfalls durch Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl, Ethyl, Methoxy oder Ethoxy, für Methylthio, Ethylthio, Methylamino, Ethylamino oder Di- methylamino.R very particularly preferably represents chlorine, in each case methyl, ethyl, methoxy or ethoxy which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, represents methylthio, ethylthio, methylamino, ethylamino or dimethylamino.
R steht ganz besonders bevorzugt für Wasserstoff, für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl oder Ethyl, oder für jeweils gegebenenfalls durch Fluor, Chlor oder Methyl substituiertes Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl.R very particularly preferably represents hydrogen, each methyl or ethyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, or cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl optionally substituted by fluorine, chlorine or methyl.
R4 steht ganz besonders bevorzugt für Wasserstoff, für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl oder Ethyl, oder für Phenyl.R 4 very particularly preferably represents hydrogen, in each case methyl or ethyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, or phenyl.
X steht ganz besonders bevorzugt für Cyano, Nitro, Fluor, Chlor, Brom, lod, oder für jeweils gegebenenfalls durch Fluor und/oder Chlor substituiertes Methyl, Ethyl, n- oder i-Propyl, Methoxy, Ethoxy, n- oder i-Propoxy, Methylthio, Ethylthio, n- oder i-Propylthio, Methylsulfinyl, Emylsulfinyl, Methylsul- fonyl oder Ethylsulfonyl, oder zwei benachbarte Gruppierungen X auch zu- sammen für eine Benzo-Gruppierung.X very particularly preferably represents cyano, nitro, fluorine, chlorine, bromine, iodine, or methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy which is optionally substituted by fluorine and / or chlorine , Methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, emylsulfinyl, methylsulfonyl or ethylsulfonyl, or two adjacent groups X also together for a benzo group.
Eine ganz besonders bevorzugte Gruppe bilden auch diejenigen Verbindungen, bei welchen Q für O (Sauerstoff) steht, R1 und R2 für Methoxy stehen und R3, R4 und X die oben als ganz besonders bevorzugte Bedeutung haben.A very particularly preferred group are also those compounds in which Q is O (oxygen), R 1 and R 2 are methoxy and R 3 , R 4 and X have the meaning particularly preferred above.
steht bevorzugt für O (Sauerstoff). 004/067518preferably represents O (oxygen). 004/067518
- 6 -- 6 -
R1 und R2 stehen am meisten bevorzugt Methoxy.R 1 and R 2 are most preferably methoxy.
R »3 steht am meisten bevorzugt für Wasserstoff.R 3 most preferably represents hydrogen.
R4 steht am meisten bevorzugt für Wasserstoff, für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl oder Ethyl.R 4 most preferably represents hydrogen, in each case methyl or ethyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy.
X steht am meisten bevorzugt für Fluor, Chlor, Brom, Methyl, Ethyl, n- oder i- Propyl, Methoxy, Ethoxy, n- oder i-Propoxy, oder zwei benachbarte Gruppierungen X auch zusammen für eine Benzo-Gruppierung.X most preferably represents fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, or two adjacent groups X together also for a benzo group.
Die neuen substituierten Pyrimidine der allgemeinen Formel (T) zeichnen sich durch starke und selektive herbizide Wirksamkeit aus.The new substituted pyrimidines of the general formula (T) are notable for strong and selective herbicidal activity.
Man erhält die neuen substituierten Pyrimidine der allgemeinen Formel (T), wenn man Pyrimidine der allgemeinen Formel (H)The new substituted pyrimidines of the general formula (T) are obtained if pyrimidines of the general formula (H)
Figure imgf000008_0001
Figure imgf000008_0001
in welcherin which
11
R und R die oben angegebene Bedeutung haben und .R and R have the meaning given above and.
Y für Halogen, Alkylthio, Alkylsulfϊnyl oder Alkylsulfonyl steht,Y represents halogen, alkylthio, alkylsulfonyl or alkylsulfonyl,
mit nucleophilen Verbindungen der allgemeinen Formel (TU) 004with nucleophilic compounds of the general formula (TU) 004
Figure imgf000009_0001
Figure imgf000009_0001
in welcherin which
n, Q, R >3 , R r>4 und X die oben angegebene Bedeutung haben,n, Q, R> 3, R r> 4 and X have the meaning given above,
gegebenenfalls in Gegenwart eines Reaktionshilfsmittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt.if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent.
Verwendet man beispielsweise 4-Difluormethoxy-6-methyl-2-methylsulfonyl-pyri- nύdin und N-Cyano-N'-(2-mercapto-phenylmethyl)-acetamidin als Ausgangsstoffe, so kann der Reaktionsablauf beim erfindungsgemäßen Verfahren durch das folgende Formelschema skizziert werden:If, for example, 4-difluoromethoxy-6-methyl-2-methylsulfonylpyrinύdin and N-cyano-N '- (2-mercapto-phenylmethyl) acetamide are used as starting materials, the course of the reaction in the process according to the invention can be outlined by the following formula become:
Figure imgf000009_0002
Figure imgf000009_0002
Die beim erfindungsgemäßen Verfahren zur Herstellung von Verbindungen der allgemeinen Formel (I) als Ausgangsstoffe zu verwendenden Pyrimidine sind durch die Formel (II) allgemein definiert. In der allgemeinen Formel (U) haben R1 und R2 vorzugsweise bzw. insbesondere diejenigen Bedeutungen, die bereits oben im Zusammenhang mit der Beschreibung der erfindungsgemäßen Verbindungen der allgemei-The pyrimidines to be used as starting materials in the process according to the invention for the preparation of compounds of the general formula (I) are: Formula (II) generally defined. In the general formula (U), R 1 and R 2 preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the general
1 nen Formel (I) vorzugsweise bzw. als insbesondere bevorzugt für R und R ange- geben worden sind; Y steht vorzugsweise für Fluor, Chlor, Brom, Methylthio, Ethylthio, Methylsulfinyl, Ethylsulfinyl, Methylsulfonyl oder Ethylsulfonyl, insbesondere für Methylsulfonyl.1 a formula (I) has been given preferably or as particularly preferred for R and R; Y preferably represents fluorine, chlorine, bromine, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, in particular methylsulfonyl.
Die Ausgangsstoffe der allgemeinen Formel (H) sind bekannt und/oder können nach an sich bekannten Verfahren hergestellt werden (vgl. J. Chem. Soc. 1957, 1830; J..The starting materials of the general formula (H) are known and / or can be prepared by processes known per se (cf. J. Chem. Soc. 1957, 1830; J ..
Org. Chem. 26, 1961, 792; US-A 3,308,119; US-A 4,711,959).Org. Chem. 26, 1961, 792; US-A 3,308,119; US-A 4,711,959).
Die beim erfindungsgemäßen Verfahren zur Herstellung von Verbindungen der allgemeinen Formel (I) weiter als Ausgangsstoffe zu verwendenden nucleophilen Ver- bindungen sind durch die Formel (TU) allgemein definiert. In der allgemeinen FormelFormula (TU) provides a general definition of the nucleophilic compounds to be used as starting materials in the process according to the invention for the preparation of compounds of the general formula (I). In the general formula
(Tu) haben Q, R3, R4 und X vorzugsweise bzw. insbesondere diejenigen Bedeutungen, die bereits oben im Zusammenhang mit der Beschreibung der erfindungsgemäßen Verbindungen der allgemeinen Formel (T) vorzugsweise bzw. als insbesondere bevorzugt für Q, R3, R4 und X angegeben worden sind.(Tu) have Q, R 3 , R 4 and X preferably or in particular those meanings which have already been mentioned above in connection with the description of the compounds of the general formula (T) according to the invention preferably or as particularly preferred for Q, R 3 , R 4 and X have been specified.
Die Ausgangsstoffe der allgemeinen Formel ( H) sind noch nicht aus der Literatur bekannt; sie sind als neue Stoffe auch Gegenstand der vorliegenden Anmeldung.The starting materials of the general formula (H) are not yet known from the literature; as new substances, they are also the subject of the present application.
Man erhält die neuen nucleophilen Verbindungen der allgemeinen Formel (JH), wenn man Arylalkylamine der allgemeinen Formel (TV)The new nucleophilic compounds of the general formula (JH) are obtained if arylalkylamines of the general formula (TV)
Figure imgf000010_0001
in welcher n, Q, R und X die oben angegebene Bedeutung haben,
Figure imgf000010_0001
in which n, Q, R and X have the meaning given above,
mit N-Cyano-imidsäureestern der allgemeinen Formel (V)with N-cyano-imidic acid esters of the general formula (V)
Figure imgf000011_0001
in welcher
Figure imgf000011_0001
in which
R3 die oben angegebene Bedeutung hat undR 3 has the meaning given above and
R für Alkyl, insbesondere für Methyl oder Ethyl steht,R represents alkyl, in particular methyl or ethyl,
gegebenenfalls in Gegenwart eines Verdünnungsmittels, wie z.B. Wasser, bei Temperaturen zwischen 0°C und 50°C umsetzt (vgl. die Herstellungsbeispiele).optionally in the presence of a diluent, e.g. Water, at temperatures between 0 ° C and 50 ° C (see the manufacturing examples).
Die als Vorprodukte benötigten Arylalkylamine der Formel (TV) sind bekannt und/oder können nach an sich bekannten Verfahren hergestellt werden (vgl. J. Am. Chem. Soc. 76 /1954, 5589-5597; Synthetic Commun. 7 (1977), 71-78; Herstellungsbeispiele).The arylalkylamines of the formula (TV) required as precursors are known and / or can be prepared by processes known per se (cf. J. Am. Chem. Soc. 76/1954, 5589-5597; Synthetic Commun. 7 (1977), 71-78; manufacturing examples).
Die weiter als Vorprodukte benötigten N-Cyano-imidsäureester der Formel (V) sind bekannte organische Synthesechemikalien.The further N-cyano-imidates of the formula (V) required as precursors are known organic synthetic chemicals.
Das erfindungsgemäße Verfahren zur Herstellung der Verbindungen der allgemeinen Formel (1) wird vorzugsweise unter Verwendung eines oder mehrerer Reaktionshilfs- mittels durchgeführt. Als Reaktionshilfsmittel für das erfindungsgemäße Verfahren kommen im Allgemeinen die üblichen anorganischen oder organischen Basen oder Säureakzeptoren in Betracht. Hierzu gehören vorzugsweise Alkalimetall- oder Erdalkalimetall- -acetate, -amide, -carbonate, -hydrogencarbonate, -hydride, -hydroxide oder -alkanolate, wie beispielsweise Natrium-, Kalium- oder Calcium-acetat, Lithium-, Natrium-, Kalium- oder Calcium-amid, Natrium-, Kalium-, Cäsium- oder Calcium-carbonat, Natrium-, Kalium- oder Calcium-hydrogencarbonat, Lithium-, Natrium-, Kalium- oder Calcium-hydrid, Lithium-, Natrium-, Kalium- oder Calcium- hydroxid, Natrium- oder Kalium- -methanolat, -ethanolat, -n- oder -i-propanolat, -n-,The process according to the invention for the preparation of the compounds of the general formula (1) is preferably carried out using one or more reaction auxiliaries. The usual inorganic or organic bases or acid acceptors are generally suitable as reaction aids for the process according to the invention. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkanolates, such as sodium, potassium or calcium acetate, lithium, sodium, potassium or calcium amide, sodium, potassium, cesium or calcium carbonate, sodium, potassium or calcium hydrogen carbonate, lithium, sodium, potassium or calcium hydride, lithium, sodium, potassium or calcium hydroxide, sodium or potassium methoxide, ethanolate, -n- or -i-propanolate, -n -
-i-, -s- oder -t-butanolat; weiterhin auch basische organische Stickstoffverbindungen, wie beispielsweise Trimemylamin, Triethylamin, Tripropylamin, Tributylamin, Ethyl-diisopropylamin, N,N-Dimethyl-cyclohexylamin, Dicyclohexylamin, Ethyl-di- cyclohexylamin, N,N-Dimethyl-anilin, N,N-Dimethyl-benzylamin, Pyridin, 2-Me- thyl-, 3-Methyl-, 4-Methyl-, 2,4-Dimethyl-, 2,6-Dimethyl-, 3,4-Dimethyl- und 3,5--i-, -s- or -t-butanolate; also basic organic nitrogen compounds, such as trimemylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N, N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N, N-dimethyl-aniline, N, N-dimethyl benzylamine, pyridine, 2-methyl, 3-methyl, 4-methyl, 2,4-dimethyl, 2,6-dimethyl, 3,4-dimethyl and 3,5-
Dimethyl-pyridin, 5-Ethyl-2-methyl-pyridin, 4-Dimethylamino-pyridin, N-Methyl- piperidin, l,4-Diazabicyclo[2,2,2]-octan (DABCO), l,5-Diazabicyclo[4,3,0]-non-5- en (DBN), oder l,8-Diazabicyclo[5,4,0]-undec-7-en (DBU).Dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo [2,2,2] octane (DABCO), 1,5-diazabicyclo [ 4,3,0] -non-5-ene (DBN), or 1,8-diazabicyclo [5,4,0] -undec-7-ene (DBU).
Das erfindungsgemäße Verfahren zur Herstellung der Verbindungen der allgemeinenThe process of the invention for the preparation of the compounds of general
Formel (I) wird vorzugsweise unter Verwendung eines oder mehrerer Verdünnungsmittel durchgeführt. Als Verdünnungsmittel zur Durchführung des erfindungsgemäßen Verfahrens kommen vor allem inerte organische Lösungsmittel in Betracht. Hierzu gehören insbesondere aliphatische, alicyclische oder aromatische, gegebenen- falls halogenierte Kohlenwasserstoffe, wie beispielsweise Benzin, Benzol, Toluol,Formula (I) is preferably carried out using one or more diluents. Inert organic solvents are particularly suitable as diluents for carrying out the process according to the invention. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene,
Xylol, Chlorbenzol, Dichlorbenzol, Petrolether, Hexan, Cyclohexan, Dichlormethan, Chloroform, Tetrachlorkohlenstoff; Ether, wie Diethylether, Diisopropylether, Dio- xan, Tetrahydrofuran oder Emylenglykoldimethyl- oder -diethylether; Ketone, wie Aceton, Butanon oder Methyl-isobutyl-keton; Nitrile, wie Acetonitril, Propionitril oder Butyronitril; Amide, wie N,N-Dimethylformamid, N,N-Dimethylacetamid, N-Xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or emylene glycol dimethyl or diethyl ether; Ketones such as acetone, butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or butyronitrile; Amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-
Methyl-formanilid, N-Methyl-pyrrolidon oder Hexamemylphosphorsäuretriamid; Ester wie Essigsäuremethylester oder Essigsäureethylester, Sulfoxide, wie Dimethyl- sulfoxid, Alkohole, wie Methanol, Ethanol, n- oder i-Propanol, Ethylenglykolmono- methylether, Ethylenglykolmonoethylether, Diethylenglykolmonomethylether, Di- ethylenglykolmonoethylether, deren Gemische mit Wasser oder reines Wasser. Die Reaktionstemperaturen können bei der Durchführung des erfindungsgemäßen Verfahrens in einem größeren Bereich variiert werden. Im Allgemeinen arbeitet man bei Temperaturen zwischen 0°C und 150°C, vorzugsweise zwischen 10°C und 120°C.Methyl formanilide, N-methyl pyrrolidone or hexamemyl phosphoric acid triamide; Esters such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide, alcohols such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water. The reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 120 ° C.
Das erfindungsgemäße Verfahren wird im Allgemeinen unter Normaldruck durchgeführt. Es ist jedoch auch möglich, das erfindungsgemäße Verfahren unter erhöhtem oder vermindertem Druck - im allgemeinen zwischen 0,1 bar und 10 bar - durchzuführen.The process according to the invention is generally carried out under normal pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressure - generally between 0.1 bar and 10 bar.
Zur Durchführung des erfindungsgemäßen Verfahrens werden die Ausgangsstoffe im Allgemeinen in angenähert äquimolaren Mengen eingesetzt. Es ist jedoch auch möglich, eine der Komponenten in einem größeren Überschuss zu verwenden. Die Umsetzung wird im allgemeinen in einem geeigneten Verdünnungsmittel in Gegenwart eines Reaktionshilfsmittels durchgeführt und das Reaktionsgemisch wird im Allgemeinen mehrere Stunden bei der erforderlichen Temperatur gerührt. Die Aufarbeitung wird nach üblichen Methoden durchgeführt (vgl. die Herstellungsbeispiele).To carry out the process according to the invention, the starting materials are generally used in approximately equimolar amounts. However, it is also possible to use one of the components in a larger excess. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary and the reaction mixture is generally stirred at the required temperature for several hours. Working up is carried out according to customary methods (cf. the production examples).
Die erfindungsgemäßen Wirkstoffe können als Defoliants, Desiccants, Krautabtö- tungsmittel und insbesondere als Unkrautvernichtungsmittel verwendet werden. Unter Unkraut im weitesten Sinne sind alle Pflanzen zu verstehen, die an Orten aufwachsen, wo sie unerwünscht sind. Ob die erfindungsgemäßen Stoffe als totale oder selektive Herbizide wirken, hängt im wesentlichen von der angewendeten Menge ab.The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers. Weeds in the broadest sense are understood to mean all plants that grow up in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
Die erfindungsgemäßen Wirkstoffe können z.B. bei den folgenden Pflanzen verwendet werden:The active compounds according to the invention can e.g. can be used in the following plants:
Dikotyle Unkräuter der Gattungen: Abutilon, Amaranthus,. Ambrosia, Anoda, An- themis, Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolyulus, Datura, Desmodium, Emex, Erysimum,Dicotyledon weeds of the genera: Abutilon, Amaranthus ,. Ambrosia, Anoda, Anthisis, Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolyulus, Datura, Desmodium, Emex, Erysimum,
Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenus Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.
Dikotyle Kulturen der Gattungen: Arachis, Beta, Brassica, Cucumis, Cucurbita, Heli- anthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Ni- cotiana, Phaseolus, Pisum, Solanum, Vicia.Dicotyledon cultures of the genera: Arachis, Beta, Brassica, Cucumis, Cucurbita, Helanthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia.
Monokotyle Unkräuter der Gattungen: Aegilops, Agropyron, Agrostis, Alopecurus,Monocotyledonous weeds of the genera: Aegilops, Agropyron, Agrostis, Alopecurus,
Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaaemum, Lolochochumem, Lolochochumem, Lolochochumum, Lolochochumum, Lolochochumum, Lolochochumem, Lolochochumum, Lolochochumum, Lolochochumum, Lolochochumum, Lolochochumum, Lolochochumum, Lolochochumum, Lolochochumum Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.
Monokotyle Kulturen der Gattungen: Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Seeale, Sorghum, Triticale, Triticum, Zea.Monocot cultures of the genera: Allium, pineapple, asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Seeale, Sorghum, Triticale, Triticum, Zea.
Die Verwendung der erfindungsgemäßen Wirkstoffe ist jedoch keineswegs auf dieseHowever, the use of the active compounds according to the invention is by no means limited to them
Gattungen beschränkt, sondern erstreckt sich in gleicher Weise auch auf andere Pflanzen.Limited genera, but extends in the same way to other plants.
Die erfindungsgemäßen Wirkstoffe eignen sich in Abhängigkeit von der Konzentra- tion zur Totalunkrautbekämpfung, z.B. auf Industrie- und Gleisanlagen und aufDepending on the concentration, the active compounds according to the invention are suitable for combating total weeds, e.g. on industrial and track systems and on
Wegen und Plätzen mit und ohne Baumbewuchs. Ebenso können die erfindungsgemäßen Wirkstoffe zur Urikrautbekämpfung in Daύerkulturen, z.B. Forst, Ziergehölz-, Obst-, Wein-, Citrus-, Nuß-, Bananen-, Kaffee-, Tee-, Gummi-, Ölpalm-, Kakao-, Beerenfrucht- und Hopfenanlagen, auf Zier- und Sportrasen und Weideflächen sowie zur selektiven Unkrautbekämpfung in einj ährigen Kulturen eingesetzt werden. Die erfindungsgemäßen Verbindungen der Formel (I) zeigen starke herbizide Wirksamkeit und ein breites Whkungsspektrum bei Anwendung auf dem Boden und auf oberirdische Pflanzenteile. Sie eignen sich in gewissem Umfang auch zur selektiven Bekämpfung von monokotylen und dikotylen Unkräutern in monokotylen und di- kotylen Kulturen, sowohl im Vorauflauf- als auch im Nachauflauf- Verfahren.Because of and places with and without tree cover. Likewise, the active compounds according to the invention for combating herbaceous weed in Daύerkulturen, for example forest, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants , on ornamental and sports turf and pasture land as well as for selective weed control in annual crops. The compounds of formula (I) according to the invention show strong herbicidal activity and a broad spectrum of activity when used on the soil and on above-ground parts of plants. To a certain extent, they are also suitable for the selective control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops, both in the pre-emergence and in the post-emergence process.
Die erfindungsgemäßen Wirkstoffe können in bestimmten Konzentrationen bzw. Aufwandmengen auch zur Bekämpfung von tierischen Schädlingen und pilzlichen oder bakteriellen Pflanzenkrankheiten verwendet werden. Sie lassen sich gegebenen- falls auch als Zwischen- oder Vorprodukte für die Synthese weiterer Wirkstoffe einsetzen.In certain concentrations or application rates, the active compounds according to the invention can also be used to control animal pests and fungal or bacterial plant diseases. If appropriate, they can also be used as intermediates or precursors for the synthesis of further active compounds.
Erfindungsgemäß können alle Pflanzen und Pflanzenteile behandelt werden. Unter Pflanzen werden hierbei alle Pflanzen und Pflanzenpopulationen verstanden, wie er- wünschte und unerwünschte Wildpflanzen oder Kulturpflanzen (einschließlich natürlich vorkommender Kulturpflanzen). Kulturpflanzen können Pflanzen sein, die durch konventionelle Züchtungs- und Optimierungsmethoden oder durch biotechnologische und gentechnologische Methoden oder Kombinationen dieser Methoden erhalten werden können, einschließlich der transgenen Pflanzen und einschließlich der durch Sortenschutzrechte schützbaren oder nicht schützbaren Pflanzensorten.According to the invention, all plants and parts of plants can be treated. Plants are understood here to mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant cultivars which can or cannot be protected by plant breeders' rights.
Unter Pflanzenteilen sollen alle oberirdischen und unterirdischen Teile und Organe der Pflanzen, wie Sproß, Blatt, Blüte und Wurzel verstanden werden, wobei beispielhaft Blätter, Nadeln, Stengel, Stämme, Blüten, Fruchtkörper, Früchte und Samen sowie Wurzeln, Knollen und Rhizome aufgeführt werden. Zu den Pflanzenteilen ge- hört auch Erntegut sowie vegetatives und generatives Vermehrungsmaterial, beispielsweise Stecklinge, Knollen, Rhizome, Ableger und Samen.Plant parts are to be understood to mean all above-ground and underground parts and organs of plants, such as shoots, leaves, flowers and roots, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.
Die erfindungsgemäße Behandlung der Pflanzen und Pflanzenteile mit den Wirkstoffen erfolgt direkt oder durch Einwirkung auf deren Umgebung, Lebensraum oder Lagerraum nach den üblichen Behandlungsmethoden, z.B. durch Tauchen, Sprühen, Verdampfen, Vernebeln, Streuen, Aufstreichen und bei Vermehrungsmaterial, insbesondere bei Samen, weiterhin durch ein- oder mehrschichtiges Umhüllen.The treatment of the plants and parts of plants with the active compounds according to the invention is carried out directly or by acting on their surroundings, living space or storage space using the customary treatment methods, for example by dipping, spraying, Evaporation, nebulization, scattering, spreading and, in the case of propagation material, in particular seeds, also by means of single- or multi-layer coating.
Die Wirkstoffe können in die üblichen Formulierungen übergeführt werden, wie Lö- sungen, Emulsionen, Spritzpulver, Suspensionen, Pulver, Stäubemittel, Pasten, lösliche Pulver, Granulate, Suspensions-Emulsions-Konzentrate, Wirkstoff-imprägnierte Natur- und synthetische Stoffe sowie Feinstverkapselungen in polymeren Stoffen.The active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances and very fine encapsulations in polymers substances.
Diese Formulierungen werden in bekannter Weise hergestellt, z. B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln und/όder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln.These formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, that is liquid solvents and / or the solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents.
Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösungsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen in Frage: Aromaten, wie Xylol, Toluol, oder Alkyl- naphthaline, chlorierte Aromaten und chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chlorethylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, mineralische und pflanzliche Öle, Alkohole, wie Butanol oder Glykol sowie deren Ether und Ester, Ketone wie Aceton, Methylethylketon, Methylisobutylketon oder Cyclohexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser.If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
Als feste Trägerstoffe kommen in Frage: z.B. Ammoniumsalze und natürliche Ge- steinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Mont- morillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate, als feste Trägerstoffe für Granulate kom- men in Frage: z.B. gebrochene und fraktionierte natürliche Gesteine wie Calcit,Possible solid carriers are: e.g. Ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite,
Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehl, Kokosnußschalen, Maiskolben und Tabakstengeln; als Emulgier- und/oder schaumerzeugende Mittel kommen in Frage: z.B. nichtionogene und anionische Emulgato- ren, wie Polyoxyethylen-Fettsäure-Ester, Polyoxyethylen-Fettalkohol-Ether, z.B. Al- kylarylpolyglykolether, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweiß- hydrolysate; als Dispergiermittel kommen in Frage: z.B. Lignin-Sulfitablaugen und Methylcellulose.Marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; Possible emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; The following may be used as dispersants: for example lignin sulfite waste liquor and methyl cellulose.
Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natürliche und synthetische pulvrige, körnige oder latexformige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospho- lipide, wie Kephaline und Lecithine und synthetische Phospholipide. Weitere Additive können mineralische und vegetabile Öle sein.Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins and synthetic phospholipids, can be used in the formulations. Other additives can be mineral and vegetable oils.
Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferro- cyanblau und organische Farbstoffe, wie Alizarin-, Azo- und Metallphthalocyanin- farbstoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden.Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 GewichtsprozentThe formulations generally contain between 0.1 and 95 percent by weight
Wirkstoff, vorzugsweise zwischen 0,5 und 90 %.Active ingredient, preferably between 0.5 and 90%.
Die erfindungsgemäßen Wirkstoffe können als solche oder in ihren Formulierungen auch in Mischung mit bekannten Herbiziden und/oder mit Stoffen, welche die Kul- turpflanzen- Verträglichkeit verbessern („Safenern") zur Unkrautbekämpfung verwendet werden, wobei Fertigformulierungen oder Tankmischungen möglich sind. Es sind also auch Mischungen mit Unkrautbekämpfungsmitteln möglich, welche ein oder mehrere bekannte Herbizide und einen Safener enthalten.The active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known herbicides and / or with substances which improve crop tolerance (“safeners”) for weed control, finished formulations or tank mixes being possible mixtures with weed control compositions which contain one or more known herbicides and a safener are also possible.
Für die Mischungen kommen bekannte Herbizide infrage, beispielsweise Acetochlor, Acifluorfen (-sodium), Aclonifen, Alachlor, Alloxydim (-sodium), Ametryne, Amicarbazone, Amidochlor, Amidosulfuron, Anilofos, Asulam, Atrazine, Azafenidin, Azimsulfuron, Beflubutamid, Benazolin (-ethyl), Benfuresate, Bensulf- uron (-methyl), Bentazon, Benzfendizone, Benzobicyclon, Benzofenap, Benzoylprop (-ethyl), Bialaphos, Bifenox, Bispyribac (-sodium), Bromobutide, Bromofenoxim,Known herbicides are suitable for the mixtures, for example Acetochlor, Acifluorfen (-sodium), Aclonifen, Alachlor, Alloxydim (-sodium), Ametryne, Amicarbazone, Amidochlor, Amidosulfuron, Anilofos, Asulam, Atrazine, Azafenidin, Azimsulfuron, Beflubutamide, Benazolin (-ethyl), Benulfureson -methyl), bentazone, benzfendizone, benzobicyclone, benzofenap, benzoylprop (-ethyl), bialaphos, bifenox, bispyribac (-sodium), bromobutide, bromofenoxime,
Bromoxynil, Butachlor, Butafenacil (-allyl), Butroxydim, Butylate, Cafenstrole, Caloxydim, Carbetamide, Carfentrazone (-ethyl), Chlomethoxyfen, Chloramben, Chloridazon, Chlorimuron (-ethyl), Chlornitrofen, Chlorsulfuron, Chlortoluron, Cini- don (-ethyl), Cinmethylin, Cinosulfuron, Clefoxydim, Clethodim, Clodinafop (-propargyl), Clomazone, Clomeprop, Clopyralid, Clopyrasulfuron (-methyl), Cloran- sulam (-methyl), Cumyluron, Cyanazine, Cybutryne, Cycloate, Cyclosulfamuron, Cycloxydim, Cyhalofop (-butyl), 2,4-D, 2,4-DB, Desmedipham, Diallate, Dicamba, Dichlorprop (-P), Diclofop (-methyl), Diclosulam, Diethatyl (-ethyl), Difenzoquat, Diflufenican, Diflufenzopyr, Dimefuron, Dimepiperate, Dimethachlor, Dimetha- metryn, Dimethenamid, Dimexyflam, Dinittamine, Diphenamid, Diquat, Dithiopyr,Bromoxynil, Butachlor, Butafenacil (-allyl), Butroxydim, Butylate, Cafenstrole, Caloxydim, Carbetamide, Carfentrazone (-ethyl), Chlomethoxyfen, Chloramben, Chloridazon, Chlorimuron (-ethyl), Chlornitrofen, Chlorsulfuron, Chlorodoluron-Cin ), Cinmethylin, Cinosulfuron, Clefoxydim, Clethodim, Clodinafop (-propargyl), Clomazone, Clomeprop, Clopyralid, Clopyrasulfuron (-methyl), Cloransulam (-methyl), Cumyluron, Cyanazine, Cybutryne, Cycloate, Cyclofoxamyl, Cyclofulfate -butyl), 2,4-D, 2,4-DB, desmedipham, dialallate, dicamba, dichloroprop (-P), diclofop (-methyl), diclosulam, diethatyl (-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, Dimepiperate, Dimethachlor, Dimethametryn, Dimethenamid, Dimexyflam, Dinittamine, Diphenamid, Diquat, Dithiopyr,
Diuron, Dymron, Epropodan, EPTC, Esprocarb, Ethalfluralin, Ethametsulfüron (-methyl), Ethofumesate, Ethoxyfen, Emoxysulfuron, Etobenzanid, Fenoxaprop (-P- ethyl), Fentrazamide, Flamprop (-isopropyl, -isopropyl-L, -methyl), Flazasulfuron, Florasulam, Fluazifop (-P-butyl), Fluazolate, Flucarbazone (-sodium), Flufenacet, Flufenpyr, Flumetsulam, Flumiclorac (-pentyl), Flumioxazin, Flumipropyn, Flumet- sulam, Fluometuron, Fluorochloridone, Fluoroglycofen (-ethyl), Flupoxam, Fluprop- acil, Flurpyrsulfuron (-methyl, -sodium), Flurenol (-butyl), Fluridone, Fluroxypyr (-butoxypropyl, -meptyl), Flurprimidol, Flurtamone, Fluthiacet (-methyl), Fluthi- arnide, Fomesafen, Foramsulfuron, Glufosinate (-ammonium), Glyphosate (-isopro- pylammonium), Halosafen, Haloxyfop (-ethoxyethyl, -P-methyl), Hexazinone, Ima- zamethabenz (-methyl), Imazamethapyr, Imazamox, Imazapic, Imazapyr, lmazaquin, Imazethapyr, Imazosulfuron, Iodosulfuron (-methyl, -sodium), Ioxynil, Isopropalin, Isόproturon, Isouron, Isoxaben, Isoxachlortole, Isoxaflutole, Isoxapyrifop, Ketospira- dox, Lactofen, Lenacil, Linuron, MCPA, Mecoprop, Mefenacet, Mesotrione, Meta- mitron, Metazachlor, Methabenzthiazuron, Metobenzuron, Metobromuron, (alpha-)Diuron, Dymron, Epropodan, EPTC, Esprocarb, Ethalfluralin, Ethametsulfüron (-methyl), Ethofumesate, Ethoxyfen, Emoxysulfuron, Etobenzanid, Fenoxaprop (-P-ethyl), Fentrazamide, Flamprop (-isopropyl, -isopropyl-L, -methyl) Flazasulfuron, Florasulam, Fluazifop (-P-butyl), Fluazolate, Flucarbazone (-sodium), Flufenacet, Flufenpyr, Flumetsulam, Flumiclorac (-pentyl), Flumioxazin, Flumipropyn, Flumet-sulam, Fluometuron, Fluorochloridone (Fluorochloridone, Flupoxam, fluprop-acil, flurpyrsulfuron (-methyl, -sodium), flurenol (-butyl), fluridone, fluroxypyr (-butoxypropyl, -meptyl), flurprimidol, flurtamone, fluthiacet (-methyl), fluthi arnide, fomesafen, foromesafen, Glufosinate (-ammonium), Glyphosate (-isopropylammonium), Halosafen, Haloxyfop (-ethoxyethyl, -P-methyl), Hexazinone, Imazamethabenz (-methyl), Imazamethapyr, Imazamox, Imazapic, Imazapyr, lmazaquin, Imazethaprone, Imazethapuron , Iodosulfuron (-methyl, -sodium), Ioxynil, Isopropalin, Isόproturon, Isouron, Isoxabe n, Isoxachlortole, Isoxaflutole, Isoxapyrifop, Ketospirox, Lactofen, Lenacil, Linuron, MCPA, Mecoprop, Mefenacet, Mesotrione, Metamitron, Metazachlor, Methabenzthiazuron, Metobenzuron, Metobromuron, (alpha-)
Metolachlor, Metosulam, Metoxuron, Metribuzin, Metsulfuron (-methyl), Molinate, Monolinuron, Naproanilide, Napropa ide, Neburon, Nicosulfuron, Norflurazon, Orbencarb, Oryzalin, Oxadiargyl, Oxadiazon, Oxasulfuron, Oxaziclomefone, Oxy- fluorfen, Paraquat, Pelargonsäure, Pendimethalin, Pendralin, Penoxysulam, Pentoxa- zone, Pethoxamid, Phenmedipham, Picolinafen, Piperophos, Pretilachlor, Primisulf- uron (-methyl), Profluazol, Profoxydim, Prometryn, Propachlor, Propanil, Propaqui- zafop, Propisochlor, Propoxycarbazone (-sodium), Propyzamide, Prosulfocarb, Pro- sulfüron, Pyraflufen (-ethyl), Pyrazogyl, Pyrazolate, Pyrazosulfüron (-ethyl), Pyraz- oxyfen, Pyribenzoxim, Pyributicarb, Pyridate, Pyridatol, Pyriftalid, Pyriminobac (-methyl), Pyrithiobac (-sodium), Quinchlorac, Quinmerac, Quinoclamine, Quizalo- fop (-P-ethyl, -P-tefuryl), Rimsulfuron, Semoxydim, Simazine, Simetryn, Sulco- trione, Sulfentrazone, Sulfometuron (-methyl), Sulfosate, Sulfosulfuron, Tebutam, Tebuthiuron, Tepraloxydim, Terbuthylazine, Terbutryn, Thenylchlor, Thiafluamide, Thiazopyr, TMdiazimin, Thifensulfuron (-methyl), Thiobencarb, Tiocarbazil, Tralkoxydim, Triallate, Triasulfuron, Tribenuron (-methyl), Triclopyr, Tridiphane, Trifluralin, Trifloxysulfuron, Triflusulfuron (-methyl), Tritosulfuron.Metolachlor, Metosulam, Metoxuron, Metribuzin, Metsulfuron (-methyl), Molinate, Monolinuron, naproanilide, napropa ide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pendralin, pentoxamidafen, pentoxamidafen, pentoxamidon, pentoxamidon, pentoxamidon, poxy , Pretilachlor, Primisulfuron (-methyl), Profluazol, Profoxydim, Prometryn, Propachlor, Propanil, Propaquizafop, Propisochlor, Propoxycarbazone (-sodium), Propyzamide, Prosulfocarb, Pro-sulfüron, Pyraflufen (-ethyl), Pyrazogyl, Pyrazolyl , Pyrazosulfüron (-ethyl), pyrazoxyfen, pyribenzoxime, pyributicarb, pyridate, pyridatol, pyriftalid, pyriminobac (-methyl), pyrithiobac (-sodium), quinchlorac, quinmerac, quinoclamine, quizalopop (-P-ethyl, -P -tefuryl), rimsulfuron, semoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron (-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim, terbuthylazine, terbutryn, thenylchlor, thiazopiazide, TM, tiazafiazide, TM hifensulfuron (-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron (-methyl), triclopyr, tridiphane, trifluralin, trifloxysulfuron, triflusulfuron (-methyl), tritosulfuron.
Für die Mischungen kommen weiterhin bekannte Safener in Frage, beispielsweise AD-67, BAS- 145138, Benoxacor, Cloquintocet (-mexyl), Cyometrinil, 2,4-D, DKA- 24, Dichlormid, Dymron, Fenclorim, Fenchlorazol (-ethyl), Flurazole, Fluxofenim, Furilazole, Isoxadifen (-ethyl), MCPA, Mecoprop (-P), Mefenpyr (-diethyl), MG-Known safeners are also suitable for the mixtures, for example AD-67, BAS-145138, Benoxacor, Cloquintocet (-mexyl), Cyometrinil, 2,4-D, DKA-24, dichlormid, Dymron, Fenclorim, Fenchlorazole (-ethyl) , Flurazole, fluxofenim, furilazole, isoxadifen (-ethyl), MCPA, mecoprop (-P), mefenpyr (-diethyl), MG-
191, Oxabetrinil, PPG-1292, R-29148.191, Oxabetrinil, PPG-1292, R-29148.
Auch eine Mischung mit anderen bekannten Wirkstoffen, wie Fungiziden, Insektiziden, Akariziden, Nematiziden, Schutzstoffen gegen Vogelfraß, Pflanzennährstoffen und Bodenstrukturverbesserungsmitteln ist möglich.A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder den daraus durch weiteres Verdünnen bereiteten Anwendungsformen, wie gebrauchsfertige Lösungen, Suspensionen, Emulsionen, Pulver, Pasten und Granulate angewandt werden. Die Anwendung geschieht in üblicher Weise, z.B. durch Gießen, Spritzen, Sprühen,The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying,
Streuen. Die erfindungsgemäßen Wirkstoffe können sowohl vor als auch nach dem Auflaufen der Pflanzen appliziert werden. Sie können auch vor der Saat in den Boden eingearbeitet werden.Sprinkle. The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be worked into the soil before sowing.
Die angewandte Wirkstoffmenge kann in einem größeren Bereich schwanken. Sie hängt im wesentlichen von der Art des gewünschten Effektes ab. Im allgemeinen liegen die Aufwandmengen zwischen 1 g und 10 kg Wirkstoff pro Hektar Bodenfläche, vorzugsweise zwischen 5 g und 5 kg pro ha.The amount of active ingredient used can vary over a wide range. It essentially depends on the type of effect desired. In general, the application rates are between 1 g and 10 kg of active ingredient per hectare of soil, preferably between 5 g and 5 kg per ha.
Wie bereits oben erwähnt, können erfindungsgemäß alle Pflanzen und deren Teile behandelt werden. In einer bevorzugten Ausführungsform werden wild vorkommende oder durch konventionelle biologische Zuchtmethoden, wie Kreuzung oder Protoplastenfüsion erhaltenen Pflanzenarten und Pflanzensorten sowie deren Teile behandelt. In einer weiteren bevorzugten Ausführungsform werden transgene Pflanzen und Pflanzensorten, die durch gentechnologische Methoden, gegebenenfalls in Kombination mit konventionellen Methoden erhalten wurden (Genetically Modified Organisms) und deren Teile behandelt. Der Begriff "Teile" bzw. "Teile von Pflanzen" oder "Pflanzenteile" wurde oben erläutert.As already mentioned above, according to the invention, all plants and their parts can be treated. In a preferred embodiment, plant species and plant cultivars which occur wildly or are obtained by conventional organic breeding methods, such as crossing or protoplast fusion, and parts thereof are treated. In a further preferred embodiment, transgenic plants and plant cultivars which have been obtained by genetic engineering methods, optionally in combination with conventional methods (genetically modified organisms) and their parts are treated. The term "parts" or "parts of plants" or "plant parts" was explained above.
Besonders bevorzugt werden erfindungsgemäß Pflanzen der jeweils handelsüblichen oder in Gebrauch befindlichen Pflanzensorten behandelt. Unter Pflanzensorten versteht man Pflanzen mit bestimmten Eigenschaften ("Traits"), die durch konventionelle Züchtung, durch Mutagenese, oder auch durch rekombinante DNA-Techniken erhalten worden sind. Dies können Sorten, Bio- und Genotypen sein.Plants of the plant varieties which are in each case commercially available or in use are particularly preferably treated according to the invention. Plant cultivars are understood to mean plants with certain properties (“traits”) which have been obtained by conventional breeding, by mutagenesis, or else by recombinant DNA techniques. These can be varieties, bio and genotypes.
Je nach Pflanzenarten bzw. Pflanzensorten, deren Standort und Wachstttmsbedin- gungen (Böden, Klima, Vegetationsperiode, Ernährung) können durch die erfindungsgemäße Behandlung auch überadditive ("synergistische") Effekte auftreten. So sind beispielsweise erniedrigte Aufwandmengen und/oder Erweiterungen des Wir- kungsspektrums und/oder eine Verstärkung der Wirkung der erfϊndungsgemäß ver- wendbaren Stoffe und Mittel - auch in Kombination mit anderen agrochemischen Wirkstoffen, besseres Wachstum der K turpflanzen, erhöhte Toleranz der Kulturpflanzen gegenüber hohen oder niedrigen Temperaturen, erhöhte Toleranz der Kulturpflanzen gegen Trockenheit oder gegen Wasser- bzw. Bodensalzgehalt, erhöhte Blühleistung, erleichterte Ernte, Beschleunigung der Reife, höhere Ernteerträge, höhere Qualität und/oder höherer Emährungswert der Ernteprodukte, höhere Lager- fahigkeit und/oder Bearbeitbarkeit der Ernteprodukte möglich, die über die eigentlich zu erwartenden Effekte hinausgehen.Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, growing season, nutrition), the treatment according to the invention can also cause superadditive ("synergistic") effects. For example, reduced application rates and / or widening of the spectrum of activity and / or an increase in the effect of the reversible substances and agents - also in combination with other agrochemical active ingredients, better growth of crop plants, increased tolerance of crop plants to high or low temperatures, increased tolerance of crop plants to dryness or to water or soil salt content, increased flowering performance, easier harvesting, acceleration the ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or processability of the harvested products, which go beyond the effects that are actually to be expected.
Zu den bevorzugten erfindungsgemäß zu behandelnden transgenen (gentechnologisch erhaltenen) Pflanzen bzw. Pflanzensorten gehören alle Pflanzen, die durch die gentechnologische Modifikation genetisches Material erhielten, welches diesen Pflanzen besondere vorteilhafte wertvolle Eigenschaften ("Traits") verleiht. Beispiele für solche Eigenschaften sind besseres Pflanzenwachstum, erhöhte Toleranz gegenüber hohen oder niedrigen Temperaturen, erhöhte Toleranz gegen Trockenheit oder gegenThe preferred transgenic (genetically engineered) plants or plant cultivars to be treated according to the invention include all plants which, by virtue of the genetic engineering modification, have received genetic material which gives these plants particularly advantageous properties (“traits”). Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to
Wasser- bzw. Bodensalzgehalt, erhöhte Blühleistung, erleichterte Ernte, Beschleunigung der Reife, höhere Ernteerträge, höhere Qualität und/oder höherer Ernährungswert der Ernteprodukte, höhere Lagerfähigkeit und/oder Bearbeitbarkeit der Ernteprodukte. Weitere und besonders hervorgehobene Beispiele für solche Eigen- schatten sind eine erhöhte Abwehr der Pflanzen gegen tierische und mikrobielleWater or soil salt content, increased flowering performance, easier harvesting, acceleration of ripening, higher harvest yields, higher quality and / or higher nutritional value of the harvested products, higher storage life and / or workability of the harvested products. Further and particularly highlighted examples of such characteristic shadows are an increased defense of the plants against animal and microbial
Schädlinge, wie gegenüber Insekten, Milben, pflanzenpathogenen Pilzen, Bakterien und/oder Viren sowie eine erhöhte Toleranz der Pflanzen gegen bestimmte herbizide Wirkstoffe. Als Beispiele transgener Pflanzen werden die wichtigen Kulturpflanzen, wie Getreide (Weizen, Reis), Mais, Soja, Kartoffel, Baumwolle, Raps sowie Obst- pflanzen (mit den Früchten Äpfel, Birnen, Zitrusfrüchten und Weintrauben) erwähnt, wobei Mais, Soja, Kartoffel, Baumwolle und Raps besonders hervorgehoben werden. Als Eigenschaften ("Traits") werden besonders hervorgehoben die erhöhte Abwehr der Pflanzen gegen Insekten durch in den Pflanzen entstehende Toxine, insbesondere solche, die durch das genetische Material aus Bacillus Thuringiensis (z.B. durch die Gene CryΙA(a), CryIA(b), CryΙA(c), CryUA, CrylUA, CryIlTß2, Cry9c Cry2Ab,Pests, such as insects, mites, phytopathogenic fungi, bacteria and / or viruses, and an increased tolerance of the plants to certain herbicidal active ingredients. Examples of transgenic plants include the important crop plants, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, rapeseed and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with corn, soybeans, potatoes , Cotton and rapeseed are highlighted. The traits are particularly emphasized as the increased defense of the plants against insects by toxins which arise in the plants, in particular those which are caused by the genetic material from Bacillus thuringiensis (for example by the genes CryΙA (a), CryIA (b), CryΙA (c), CryUA, CrylUA, CryIlTß2, Cry9c Cry2Ab,
Cry3Bb und CrylF sowie deren Kombinationen) in den Pflanzen erzeugt werden (im folgenden "Bt Pflanzen"). Als Eigenschaften ("Traits") werden auch besonders hervorgehoben die erhöhte Abwehr von Pflanzen gegen . Pilze, Bakterien und Viren durch Systemische Akquirierte Resistenz (SAR), Systemin, Phytoalexine, Elicitoren sowie Resistenzgene und entsprechend exprimierte Proteine und Toxine. Als Eigen- schatten ("Traits") werden weiterhin besonders hervorgehoben die erhöhte Toleranz der Pflanzen gegenüber bestimmten herbiziden Wirkstoffen, beispielsweise Imid- azolinonen, Sulfonylharnstoffen, Glyphosate oder Phosphinothricin (z.B. "PAT"- Gen). Die jeweils die gewünschten Eigenschaften ("Traits") verleihenden Gene können auch in Kombinationen miteinander in den transgenen Pflanzen vorkommen. Als Beispiele für "Bt Pflanzen" seien Maissorten, Baumwollsorten, Sojasorten und Kartoffelsorten genannt, die unter den Handelsbezeichnungen YLELD GARD® (z.B. Mais, Baumwolle, Soja), KnockOut® (z.B. Mais), StarLink® (z.B. Mais), Bollgard® (Baumwolle), Nucotn® (Baumwolle) und NewLeaf® (Kartoffel) vertrieben werden. Als Beispiele für Herbizid-tolerante Pflanzen seien Maissorten, Baumwollsorten und Sojasorten genannt, die unter den Handelsbezeichnungen Roundup Ready® (Töleranz gegen Glyphosate z.B. Mais, Baumwolle, Soja), Liberty Link® (Toleranz gegen Phosphinothricin, z.B. Raps), EVA® (Toleranz gegen Imidazolinone) und STS® (Toleranz gegen Sulfonylharnstoffe z.B. Mais) vertrieben werden. Als Herbizid-re- sistente (konventionell auf Herbizid-Toleranz gezüchtete) Pflanzen seien auch die unter der Bezeichnung Clearfield® vertriebenen Sorten (z.B. Mais) erwähnt. Selbstverständlich gelten diese Aussagen auch für in der Zukunft entwickelte bzw. zukünftig auf den Markt kommende Pflanzensorten mit diesen oder zukünftig entwickelten genetischen Eigenschaften ("Traits").Cry3Bb and CrylF and their combinations) are generated in the plants (in following "Bt plants"). The increased defense of plants against are also particularly emphasized as traits. Fungi, bacteria and viruses through systemic acquired resistance (SAR), systemin, phytoalexins, elicitors as well as resistance genes and correspondingly expressed proteins and toxins. The increased tolerance of the plants to certain herbicidal active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinothricin (for example “PAT” gene), is also particularly emphasized as characteristic traits. The genes conferring the desired properties ("traits") can also occur in combinations with one another in the transgenic plants. Examples of "Bt plants" are maize varieties, cotton varieties, soy varieties and potato varieties that are sold under the trade names YLELD GARD® (e.g. corn, cotton, soy), KnockOut® (e.g. corn), StarLink® (e.g. corn), Bollgard® ( Cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants are corn varieties, cotton varieties and soy varieties that are sold under the trade names Roundup Ready® (tolerance to glyphosate e.g. corn, cotton, soy), Liberty Link® (tolerance to phosphinothricin, e.g. rapeseed), EVA® (tolerance against imidazolinones) and STS® (tolerance to sulfonylureas such as corn). Also worth mentioning as herbicide-resistant plants (conventionally grown to herbicide tolerance) are the varieties sold under the name Clearfield® (for example maize). Of course, these statements also apply to plant varieties developed in the future or coming onto the market in the future with these or future-developed genetic properties ("traits").
, .Die aufgeführten Pflanzen können besonders vorteilhaft erfindungsgemäß mit den Verbindungen der allgemeinen Formel I bzw. den erfindungsgemäßen Wirkstoffmi- schungen behandelt werden, wobei zusätzlich zu der guten Bekämpfung der Unkraut- pflanzen die oben genannten synergistischen Effekte mit den transgenen Pflanzen oder Pflanzensorten auftreten. Die bei den Wirkstoffen bzw. Mischungen oben ange- gebenen Vorzugsbereiche gelten auch für die Behandlung dieser Pflanzen. Besonders hervorgehoben sei die Pflanzenbehandlung mit den im vorliegenden Text speziell aufgeführten Verbindungen bzw. Mischungen.The plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula I or the active compound mixtures according to the invention, the synergistic effects mentioned above occurring with the transgenic plants or plant cultivars in addition to the good control of the weed plants. The preferred ranges given above for the active ingredients or mixtures also apply to the treatment of these plants. Especially plant treatment with the compounds or mixtures specifically listed in the present text should be emphasized.
Die Herstellung und die Verwendung der erfindungsgemäßen Wirkstoffe geht aus den nachfolgenden Beispielen hervor. The preparation and use of the active compounds according to the invention can be seen from the examples below.
Herstellungsbeispiele:Preparation Examples:
Beispiel 1example 1
2,23 g (10 mMol) N-Cyano-N'-(6-chlor-2-hydroxy-phenylmethyl)-acetamidin werden bei Raumtemperatur (ca. 20°C) in 50 ml Toluol vorgelegt und unter Rühren nacheinander mit 4,14 g (30 mMol) Calciumcarbonat und 2,18 g (10 mMol) 4,6-Di- methoxy-2-methylsulfoήyl-pyrimidin versetzt. Die Reaktionsmischung wird dann 12 Stunden unter Rühren zum Rückfluß erhitzt. Anschließend wird unter vermindertem2.23 g (10 mmol) of N-cyano-N '- (6-chloro-2-hydroxy-phenylmethyl) -acetamidine are initially introduced into 50 ml of toluene at room temperature (approx. 20 ° C) and, with stirring, 14 g (30 mmol) of calcium carbonate and 2.18 g (10 mmol) of 4,6-dimethoxy-2-methylsulfoήyl-pyrimidine were added. The reaction mixture is then heated to reflux with stirring for 12 hours. Then it is reduced
Druck eingeengt, der Rückstand mit 100 ml Wasser versetzt und dreimal mit je 50 ml Essigsäureethylester extrahiert. Die vereinigten organischen Phasen werden mit Wasser gewaschen, mit Natriumsulfat getrocknet und filtriert. Das Filtrat wird unter vermindertem Druck eingeengt, der Rückstand mit Diethylether digeriert und das hierbei kristallin angefallene Produkt durch Absaugen isoliert.Concentrated pressure, the residue was mixed with 100 ml of water and extracted three times with 50 ml of ethyl acetate. The combined organic phases are washed with water, dried with sodium sulfate and filtered. The filtrate is concentrated under reduced pressure, the residue is digested with diethyl ether and the product obtained in crystalline form is isolated by suction.
Man erhält 0,90 g (25 % der Theorie) N-Cyano-N'-[6-chlor-2-(4,6-dimethoxy-pyri- midm-2-yl-oxy)-phenylmethyl]-acetamidin. logP = 2,19 a) 0.90 g (25% of theory) of N-cyano-N '- [6-chloro-2- (4,6-dimethoxy-pyrimidm-2-yl-oxy) -phenylmethyl] -acetamidine are obtained. logP = 2.19 a)
Analog zu Herstellungsbeispiel 1 und entsprechend der allgemeinen Beschreibung des erfindungsgemäßen Herstellungsverfahrens können beispielsweise auch die in der nachstehenden Tabelle 1 aufgeführten Verbindungen der Formel (I) hergestellt werden.
Figure imgf000025_0001
Analogously to Preparation Example 1 and in accordance with the general description of the preparation process according to the invention, it is also possible, for example, to prepare the compounds of the formula (I) listed in Table 1 below.
Figure imgf000025_0001
Figure imgf000025_0002
Figure imgf000025_0002
Figure imgf000026_0001
Figure imgf000026_0001
Die Bestimmung der in der Tabelle angegebenen logP- Werte erfolgte gemäß EEC-The logP values specified in the table were determined in accordance with EEC
Directive 79/831 Annex V.A8 durch HPLC (High Performance Liquid Chromato- graphy) an einer Phasenumkehrsäule (C 18). Temperatur: 43 °C.Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a phase reversal column (C 18). Temperature: 43 ° C.
(a) Eluenten für die Bestimmung im sauren Bereich: 0,1 % wässrige Phosphorsäure,(a) eluents for determination in the acidic range: 0.1% aqueous phosphoric acid,
Acetonitril; linearer Gradient von 10% Acetonitril bis 90 % Acetonitril - entsprechende Messergebnisse sind in Tabelle 1 mit a) markiert.acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile - corresponding measurement results are marked in Table 1 with a ).
(b) Eluenten für die Bestimmung im neutralen Bereich: 0,01 -molare wässrige Phosphatpuffer-Lösung, Acetonitril; linearer Gradient von 10 % Acetonitril bis 90 % Acetonitril - entsprechende Messergebnisse sind in Tabelle 1 mit b) markiert.(b) eluents for determination in the neutral range: 0.01 molar aqueous phosphate buffer solution, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile - corresponding measurement results are marked in Table 1 with b).
Die Eichung erfolgte mit unverzweigten Alkan-2-onen (mit 3 bis 16 Kohlenstoff- atomen), deren logP-Werte bekannt sind (Bestimmung der logP- Werte anhand derThe calibration was carried out using unbranched alkan-2-ones (with 3 to 16 carbon atoms) whose logP values are known (determination of the logP values using the
Retentionszeiten durch lineare Interpolation zwischen zwei aufeinanderfolgenden Alkanonen).Retention times by linear interpolation between two consecutive alkanones).
Die lambda-max- Werte wurden an Hand der UV-Spektren von 200 nm bis 400 nm in den Maxima der chromatographischen Signale ermittelt. Ausgangsstoffe der Formel (HD:The lambda max values were determined on the basis of the UV spectra from 200 nm to 400 nm in the maxima of the chromatographic signals. Starting materials of the formula (HD:
Beispiel (JE-l)Example (JE-l)
Figure imgf000027_0001
Figure imgf000027_0001
Staffelrelay
Figure imgf000027_0002
Figure imgf000027_0002
13,8 g (0,20 Mol) Hydroxylamin-Hydrochlorid werden in 50 ml Wasser gelöst, bei Raumtemperatur (ca. 20°C) unter Rühren mit 25 (0,16 Mol) 6-Chlor-2-hydroxy- benzaldehyd portionsweise versetzt und dann mit einer Lösung von 10,6 g (0,10 Mol) Natriumcarbonat in 50 ml Wasser tropfenweise versetzt, wobei die Reaktionstemperatur bei maximal 45°C gehalten wird. Die Reaktionsmischung wird 12 Stunden bei Raumtemperatur gerührt. Anschließend wird das Rohprodukt durch Ab- saugen isoliert, in Methylenchlorid aufgenommen, mit Wasser gewaschen, mit Natriumsulfat getrocknet und filtriert. Das Filtrat wird unter vermindertem Druck eingeengt, der Rückstand mit Diethylether digeriert und das kristalline Produkt durch Absaugen isoliert.13.8 g (0.20 mol) of hydroxylamine hydrochloride are dissolved in 50 ml of water, 25 (0.16 mol) of 6-chloro-2-hydroxybenzaldehyde are added in portions at room temperature (about 20.degree. C.) while stirring and then a solution of 10.6 g (0.10 mol) of sodium carbonate in 50 ml of water was added dropwise, the reaction temperature being kept at a maximum of 45 ° C. The reaction mixture is stirred for 12 hours at room temperature. The crude product is then isolated by suction, taken up in methylene chloride, washed with water, dried with sodium sulfate and filtered. The filtrate is concentrated under reduced pressure, the residue is digested with diethyl ether and the crystalline product is isolated by suction.
Man erhält 24 g (88 % der Theorie) 6-Chlor-2-hydroxy-benzaldoxim vom Schmelzpunkt 161°C.24 g (88% of theory) of 6-chloro-2-hydroxy-benzaldoxime with a melting point of 161 ° C. are obtained.
Analog erhält man beispielsweise 2-Hydroxy-benzaldoxim (Fp.: 80°C), 2-Hydroxy- 3-methoxy-5-methyl-benzaldoxim (Fp.: 166°C), 2-Hydroxy-5-methyl-benzaldoxim (Fp.: 108°C), 2-Hydroxy-3-methoxy-benzaldoxim (Fp.: 127°C) 2-Hydroxy-5-me- thoxy-benzaldoxim (Fp.: 122°C), 2-Hydroxy-5-brom-benzaldoxim (Fp.: 128°C), 2- Hydroxy-5-chlor-benzaldoxim (Fp.: 122°C), 2-Hydroxy-5-nitro-benzaldoxim (Fp.: 243 °C), 2-Hydroxy-3,5-dicHor-benzaldoxim, 2-Hydroxy-3-ethoxy-benzaldoxim (Fp.: 100°C), 2-Hydroxy-3-methyl-benzaldoxim (Fp.: 96°C) und 2-Hydroxy-l- naphthaldoxim.Analogously, for example, 2-hydroxy-benzaldoxime (m.p .: 80 ° C), 2-hydroxy-3-methoxy-5-methyl-benzaldoxime (m.p .: 166 ° C), 2-hydroxy-5-methyl-benzaldoxime ( M.p .: 108 ° C), 2-hydroxy-3-methoxy-benzaldoxime (m.p .: 127 ° C) 2-hydroxy-5-me- thoxy-benzaldoxime (m.p .: 122 ° C), 2-hydroxy-5-bromobenzaldoxim (m.p .: 128 ° C), 2-hydroxy-5-chloro-benzaldoxim (m.p .: 122 ° C), 2- Hydroxy-5-nitro-benzaldoxime (m.p .: 243 ° C), 2-hydroxy-3,5-dicHor-benzaldoxime, 2-hydroxy-3-ethoxy-benzaldoxime (m.p .: 100 ° C), 2-hydroxy- 3-methyl-benzaldoxime (m.p .: 96 ° C) and 2-hydroxy-1-naphthaldoxime.
Stufe 2Level 2
Figure imgf000028_0001
Figure imgf000028_0001
23 g (0,135 Mol) 6-Chlor-2-hydroxy-benzaldoxim werden in 100 ml Essigsäure23 g (0.135 mol) of 6-chloro-2-hydroxy-benzaldoxime are dissolved in 100 ml of acetic acid
(„Eisessig") gelöst und bei Raumtemperatur (ca. 20°C) unter Rühren mit 43,8 g (0,673 Mol) Zink (Staub) portionsweise versetzt. Die Reaktionsmischung wird 12 Stunden bei Raumtemperatur gerührt, abgesaugt und mit Eisessig nachgewaschen. Das Filtrat wird unter vermindertem Druck eingeengt, der Rückstand mit Essigsäure- ethylester verrührt und abgesaugt. Das Festprodukt wird in Wasser gelöst und mit("Glacial acetic acid") and 43.8 g (0.673 mol) of zinc (dust) were added in portions at room temperature (approx. 20 ° C.) with stirring. The reaction mixture was stirred at room temperature for 12 hours, suction filtered and washed with glacial acetic acid The filtrate is concentrated under reduced pressure, the residue is stirred with ethyl acetate and suction filtered, and the solid product is dissolved in water and washed with
25%iger wässriger Ammoniaklösung alkalisch gestellt. Das hierbei kristallin angefallene Produkt wird dann durch Absaugen isoliert.25% aqueous ammonia solution made alkaline. The product obtained in crystalline form is then isolated by suction.
Man erhält 13,5 g (64 % der Theorie) 6-Chlor-2-hydroxy-benzylamin vom Schmelz- punkt 149°C.13.5 g (64% of theory) of 6-chloro-2-hydroxy-benzylamine with a melting point of 149 ° C. are obtained.
Analog erhält man beispielsweise 2-Hydroxy-benzylamin (Fp.: 128°C), 2-Hydroxy- 3-methoxy-5-methyl-benzylamin (Fp.: 159°C), 2-Hydroxy-5-memyl-benzylamin (Fp.: 176°C), 2-Hydroxy-3-methoxy-benzylamin (Fp.: 149°C), 2-Hydroxy-5-me- thoxy-benzylamin (Fp.: 128°C), 2-Hydroxy-5-brom-benzylamin (Fp.: 230°C), 2-Hy- choxy-5-cMor-berιzyιamin (Fp.: 187°C), 2-Hychoxy-3,5-dicMor-benzylamin (Fp.: 216°C), 2-Hydroxy-3-ethoxy-benzylamin (Fp.: 105°C), 2-Hydroxy-3-methyl-benzyl- amin und 2-Hydroxy-l-naphthylmemylamin. Stufe 3Analogously, 2-hydroxy-benzylamine (mp: 128 ° C), 2-hydroxy-3-methoxy-5-methyl-benzylamine (mp: 159 ° C), 2-hydroxy-5-memyl-benzylamine ( M.p .: 176 ° C), 2-hydroxy-3-methoxy-benzylamine (m.p .: 149 ° C), 2-hydroxy-5-methoxy-benzylamine (m.p .: 128 ° C), 2-hydroxy- 5-bromo-benzylamine (m.p .: 230 ° C), 2-hychoxy-5-cMor-berιzyιamin (m.p .: 187 ° C), 2-hychoxy-3,5-dicMor-benzylamine (m.p .: 216 ° C), 2-hydroxy-3-ethoxy-benzylamine (mp: 105 ° C), 2-hydroxy-3-methyl-benzylamine and 2-hydroxy-l-naphthylmemylamine. level 3
Figure imgf000029_0001
Figure imgf000029_0001
Eine Mischung aus 3,14 g (20 mMol) 6-CWor-2-hydroxy-berιzylamin, 1,96 g (20 mMol) N-Cyano-iminoessigsäure-methylester und 30 ml Wasser wird 12 Stunden bei Raumtemperatur (ca. 20°C) gerührt. Das kristallin angefallene Produkt wird dann durch Absaugen isoliert.A mixture of 3.14 g (20 mmol) of 6-CWor-2-hydroxy-berιzylamin, 1.96 g (20 mmol) of N-cyano-iminoacetic acid methyl ester and 30 ml of water is 12 hours at room temperature (about 20 ° C) stirred. The crystalline product is then isolated by suction.
Man erhält 2,8 g (63 % der Theorie) N-Cyano-N'-(6-chlor-2-hydroxy-phenylmethyl)- acetamidin vom Schmelzpunkt 184°C.2.8 g (63% of theory) of N-cyano-N '- (6-chloro-2-hydroxy-phenylmethyl) acetamidine with a melting point of 184 ° C. are obtained.
Analog zu Beispiel (ULI) können beispielsweise auch die in der nachstehenden Tabelle 1 aufgeführten Verbindungen der Formel (I) hergestellt werden.Analogously to Example (ULI), for example, the compounds of the formula (I) listed in Table 1 below can also be prepared.
Figure imgf000029_0002
Figure imgf000029_0002
Tabelle 1; Beispiele für die Verbindungen der Formel (IH)Table 1; Examples of the compounds of the formula (IH)
Figure imgf000029_0003
Figure imgf000029_0003
Figure imgf000030_0001
Anwendungsbeispiele:
Figure imgf000030_0001
Application examples:
Beispiel AExample A
Pre-emergence-TestPre-emergence test
Lösungsmittel: 5 Gewichtsteile AcetonSolvent: 5 parts by weight of acetone
Emulgator: 1 Gewichtsteil AlkylarylpolyglykoletherEmulsifier: 1 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel, gibt die angegebene Menge Emulgator zu und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Samen der Testpflanzen werden in normalen Boden ausgesät. Nach 24 Stunden wird der Boden so mit der Wirkstoffzubereitung besprüht, dass die jeweils gewünschte Wirkstoffmenge pro Flächeneinheit ausgebracht wird. Die Wirkstoffkonzentration in der Spritzbrühe wird so gewählt, dass in 1000 Liter Wasser pro Hektar die jeweils gewünschte Wirkstoffmenge ausgebracht wird.Seeds of the test plants are sown in normal soil. After 24 hours, the soil is sprayed with the active ingredient preparation in such a way that the desired amount of active ingredient is applied per unit area. The active ingredient concentration in the spray liquor is chosen so that the desired amount of active ingredient is applied in 1000 liters of water per hectare.
Nach drei Wochen wird der Schädigungsgrad der Pflanzen bonitiert in % Schädigung im Vergleich zur Entwicklung der unbehandelten Kontrolle. Es bedeuten:After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control. It means:
0 % = keine Wirkung (wie unbehandelte Kontrolle) 100 % = totale Vernichtung0% = no effect (like untreated control) 100% = total destruction
In diesem Test zeigen beispielsweise die Verbindungen gemäß Herstellungsbeispiel 2 und 5 bei zum Teil guter Verträglichkeit gegenüber Kulturpflanzen, wie z.B. Mais, Raps und Zuckerrüben, starke Wirkung gegen Unkräuter. Beispiel BIn this test, for example, the compounds according to Preparation Examples 2 and 5, with good tolerance to crop plants, such as, for example, maize, oilseed rape and sugar beet, show a strong action against weeds. Example B
Post-emergence-TestPost-emergence test
Lösungsmittel: 5 Gewichtsteile AcetonSolvent: 5 parts by weight of acetone
Emulgator: 1 Gewichtsteil AlkylarylpolyglykoletherEmulsifier: 1 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel, gibt die angegebene Menge Emulgator zu und verdünnt das Konzentrat mit Wasser auf die gewünschteTo produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired level
Konzentration.Concentration.
Mit der Wirkstoffzubereitung spritzt man Testpflanzen, welche eine Höhe von 5 - 15 cm haben so, dass die jeweils gewünschten Whkstoffmengen pro Flächenein- heit ausgebracht werden. Die Konzentration der Spritzbrühe wird so gewählt, dass inTest plants with a height of 5 - 15 cm are sprayed with the active ingredient preparation in such a way that the desired quantities of active substances are applied per unit area. The concentration of the spray liquor is chosen so that in
1000 1 Wasser/ha die jeweils gewünschten Wkkstoffmengen ausgebracht werden.1000 1 water / ha, the desired quantities of material are applied.
Nach drei Wochen wird der Schädigungsgrad der Pflanzen bonitiert in % Schädigung im Vergleich zur Entwicklung der unbehandelten Kontrolle.After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.
Es bedeuten:It means:
0 % = keine Wirkung (wie unbehandelte Kontrolle) 100 % = totale Vernichtung0% = no effect (like untreated control) 100% = total destruction
In diesem Test zeigen beispielsweise die Verbindungen gemäß Herstellungsbeispiel 2, 5, 10 und 12 bei zum Teil guter Verträglichkeit gegenüber Kulturpflanzen, wie z.B. Mais und Zuckerrüben, starke Wirkung gegen Unkräuter. In this test, for example, the compounds according to Preparation Examples 2, 5, 10 and 12 show some of which are well tolerated by crop plants, such as e.g. Corn and sugar beet, strong weed control.

Claims

PatentansprfichePatentansprfiche
1. Substituierte Pyrimidine der allgemeinen Formel (T)1. Substituted pyrimidines of the general formula (T)
Figure imgf000033_0001
Figure imgf000033_0001
in welcherin which
n für die Zahlen 0, 1 oder 2 steht,n represents the numbers 0, 1 or 2,
Q für O (Sauerstoff) oder S (Schwefel) steht,Q represents O (oxygen) or S (sulfur),
R1 für Wasserstoff, für Halogen, oder für jeweils gegebenenfalls substituiertes Alkyl, Alkoxy, Alkylthio, Alkylarnino oder Dialkylamino steht,R 1 represents hydrogen, halogen or optionally substituted alkyl, alkoxy, alkylthio, alkylarnino or dialkylamino,
R für Wasserstoff, für Halogen, oder für jeweils gegebenenfalls substituiertes Alkyl, Alkoxy, Alkylthio, Alkylarnino oder Dialkylamino steht,R represents hydrogen, halogen or optionally substituted alkyl, alkoxy, alkylthio, alkylarnino or dialkylamino,
R für Wasserstoff oder für jeweils gegebenenfalls substituiertes Alkyl oder Cycloalkyl steht,R stands for hydrogen or for optionally substituted alkyl or cycloalkyl,
R4 für Wasserstoff oder für jeweils gegebenenfalls substituiertes Alkyl oder Phenyl steht, undR 4 represents hydrogen or represents optionally substituted alkyl or phenyl, and
. X für Cyano, Nitro, Halogen oder für jeweils gegebenenfalls substitu- iertes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl steht, oder zwei be- nachbarte Gruppierungen X auch zusammen für eine Benzo-Gruppie- rung stehen., X stands for cyano, nitro, halogen or for optionally optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, or two neighboring groups X also stand together for a benzo group.
2. Verbindungen gemäß Anspruch 1, dadurch gekennzeichnet, dass2. Compounds according to claim 1, characterized in that
R1 für Wasserstoff, für Halogen, für jeweils gegebenenfalls durch Halogen oder d-C4- Alkoxy substituiertes Alkyl oder Alkoxy mit jeweils 1 bis 6 Kohlenstoffatomen in den Alkylgruppen, oder für Alkylthio, Alkylarnino oder Dialkylamino mit jeweils 1 bis 6 Kohlenstoffatomen in den Alkylgruppen steht,R 1 represents hydrogen, halogen, alkyl or alkoxy each optionally substituted by halogen or dC 4 -alkoxy, each having 1 to 6 carbon atoms in the alkyl groups, or alkylthio, alkylarnino or dialkylamino each having 1 to 6 carbon atoms in the alkyl groups,
R2 für Wasserstoff, für Halogen, für jeweils gegebenenfalls durch Halogen oder d-C4- Alkoxy substituiertes Alkyl oder Alkoxy mit jeweils 1 bis 6 Kohlenstoffatomen in den Alkylgruppen, oder für Alkylthio, Al- kylamino oder Dialkylamino mit jeweils 1 bis 6 Kohlenstoffatomen in den Alkylgruppen steht,R 2 for hydrogen, for halogen, for alkyl or alkoxy each optionally substituted by halogen or dC 4 -alkoxy, each having 1 to 6 carbon atoms in the alkyl groups, or for alkylthio, alkylamino or dialkylamino each having 1 to 6 carbon atoms in the alkyl groups stands,
R3 für Wasserstoff, für gegebenenfalls durch Cyano, Halogen oder C1-C4-R 3 for hydrogen, for optionally by cyano, halogen or C 1 -C 4 -
Alkoxy substituiertes Alkyl mit 1 bis 6 Kohlenstoffatomen, oder für gegebenenfalls durch Cyano, Halogen oder Ci-C -Alkyl substituiertesAlkoxy-substituted alkyl having 1 to 6 carbon atoms, or substituted or unsubstituted or substituted by cyano, halogen or C 1 -C 4 -alkyl
Cycloalkyl mit 3 bis 6 Kohlenstoffatomen steht,Cycloalkyl having 3 to 6 carbon atoms,
R4 für Wasserstoff, für gegebenenfalls durch Cyano, Halogen oder CrC4-R 4 for hydrogen, for optionally by cyano, halogen or CrC 4 -
Alkoxy substituiertes Alkyl mit 1 bis 6 Kohlenstoffatomen, oder für gegebenenfalls durch Nitro, Cyano, Halogen, Ci-Q-Alkyl, CjrC4-Alkoxy substituted alkyl with 1 to 6 carbon atoms, or for optionally by nitro, cyano, halogen, Ci-Q-alkyl, CjrC 4 -
Halogenalkyl, Ci-C4-Alkoxy oder CrQ-Halogenalkoxy substituiertes Phenyl steht, undHaloalkyl, Ci-C 4 alkoxy or CrQ-haloalkoxy substituted phenyl, and
X für Cyano, Nitro, Halogen oder für jeweils gegebenenfalls durch Halogen substituiertes Alkyl, Alkoxy, Alkylthio, Alfylsulfϊnyl oderX for cyano, nitro, halogen or for in each case optionally substituted by halogen alkyl, alkoxy, alkylthio, alfylsulfonyl or
Alkylsulfonyl mit 1 bis 6 Kohlenstoffatomen steht, oder zwei benach- barte Gruppierungen X auch zusammen für eine Benzo-Gruppierung stehen.Alkylsulfonyl having 1 to 6 carbon atoms, or two adjacent bearded groupings X also stand together for a benzo grouping.
3. Verbindungen gemäß Anspruch 1, dadurch gekennzeichnet, dass3. Compounds according to claim 1, characterized in that
R1 für Wasserstoff, für Fluor, Chlor, Brom, lod, für jeweils gegebenenfalls durch Fluor, Chlor, Methoxy, Ethoxy, n- oder i-Propoxy substituiertes Methyl, Ethyl, n- oder i-Propyl, Methoxy, Ethoxy, n- oder i- Propoxy, für Methylthio, Ethylthio, n- oder i-Propylthio, Methyl- amino, Ethylamino, n- oder i-Propylamino, Dimethylamino oder Di- ethylamino steht,R 1 for hydrogen, for fluorine, chlorine, bromine, iodine, for methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- each optionally substituted by fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy or i-propoxy, represents methylthio, ethylthio, n- or i-propylthio, methylamino, ethylamino, n- or i-propylamino, dimethylamino or diethylamino,
R2 für Wasserstoff, für Fluor, Chlor, Brom, lod, für jeweils gegebenenfalls durch Fluor, Chlor, Methoxy, Ethoxy, n- oder i-Propoxy substitu- iertes Methyl, Ethyl, n- oder i-Propyl, Methoxy, Ethoxy, n- oder i-R 2 for hydrogen, for fluorine, chlorine, bromine, iodine, for each methyl, ethyl, n- or i-propyl, methoxy, ethoxy optionally substituted by fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, n- or i-
Propoxy, für Methylthio, Ethylthio, n- oder i-Propylthio, Methylamino, Ethylamino, n- oder i-Propylamino, Dimethylamino oder Di- emyla ino steht,Propoxy, represents methylthio, ethylthio, n- or i-propylthio, methylamino, ethylamino, n- or i-propylamino, dimethylamino or dimethylamino,
R3 für Wasserstoff, für jeweils gegebenenfalls durch Cyano, Fluor, Chlor,R 3 for hydrogen, for each optionally by cyano, fluorine, chlorine,
Methoxy, Ethoxy, n- oder i-Propoxy substituiertes Methyl, Ethyl, n- oder i-Propyl, oder für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methyl, Ethyl, n- oder i-Propyl substituiertes Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl steht,Methoxy, ethoxy, n- or i-propoxy substituted methyl, ethyl, n- or i-propyl, or for cyclopropyl, cyclobutyl, cyclopentyl or optionally substituted in each case by cyano, fluorine, chlorine, methyl, ethyl, n- or i-propyl Cyclohexyl stands,
R4 für Wasserstoff, für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy, Ethoxy, n- oder i-Propoxy substituiertes Methyl, Ethyl, n- oder i-Propyl, oder für gegebenenfalls durch Nitro, Cyano, Fluor, Chlor, Brom, Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Trifluormethyl, Methoxy, Ethoxy, n- oder i-Propoxy, Difluormethoxy oder Trifluormethoxy substituiertes Phenyl steht, und X für Cyano, Nitro, Fluor, Chlor, Brom, lod, oder für jeweils gegebenenfalls durch Fluor und/oder Chlor substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Methoxy, Ethoxy, n- oder i-Propoxy, n-, i-, s- oder t-Butoxy, Methylthio, Ethylthio, n- oder i-Propylthio,R 4 for hydrogen, for each methyl, ethyl, n- or i-propyl optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, or for optionally by nitro, cyano, fluorine, chlorine, bromine , Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy substituted phenyl, and X for cyano, nitro, fluorine, chlorine, bromine, iodine, or for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, each optionally substituted by fluorine and / or chlorine , Ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio,
Methylsulfinyl, Ethylsulfinyl, n- oder i-Prόpylsulfinyl, Methylsulfonyl oder Ethylsulfonyl steht, oder zwei benachbarte Gruppierungen X auch zusammen für eine Benzo-Gruppierung stehen.Methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl or ethylsulfonyl, or two adjacent X groups together also represent a benzo group.
Verfahren zur Herstellung der Verbindungen gemäß Anspruch 1, dadurch gekennzeichnet, dass Pyrimidine der allgemeinen Formel (IT)Process for the preparation of the compounds according to claim 1, characterized in that pyrimidines of the general formula (IT)
Figure imgf000036_0001
Figure imgf000036_0001
in welcherin which
R » 1 ™ und R die in Anspruch 1 angegebene Bedeutung haben undR »1 ™ and R have the meaning given in claim 1 and
Y für Halogen, Alkylthio, Alkylsulfinyl oder Alkylsulfonyl steht,Y represents halogen, alkylthio, alkylsulfinyl or alkylsulfonyl,
mit nucleophilen Verbindungen der allgemeinen Formel (Tfl)with nucleophilic compounds of the general formula (Tfl)
Figure imgf000036_0002
004/067518
Figure imgf000036_0002
004/067518
3535
in welcherin which
n, Q, R , R und X die in Anspruch 1 angegebene Bedeutung haben,n, Q, R, R and X have the meaning given in claim 1,
gegebenenfalls in Gegenwart eines Reaktionshilfsmittels und gegebenenfalls in Gegenwärt eines Verdünnungsmittels umgesetzt werden.optionally in the presence of a reaction auxiliary and optionally in the presence of a diluent.
5. Verwendung von mindestens einer Verbindung gemäß Anspruch 1 zum Bekämpfen von unerwünschten Pflanzen.5. Use of at least one compound according to claim 1 for controlling unwanted plants.
6. Herbizides Mittel, gekennzeichnet durch einen Gehalt an einer Verbindung gemäß Anspruch 1 und üblichen Streckmitteln und/oder oberflächenaktiven Mitteln.6. Herbicidal agent, characterized by a content of a compound according to claim 1 and conventional extenders and / or surface-active agents.
7. Verfahren zum Bekämpfen von unerwünschtem Pflanzenwuchs, dadurch gekennzeichnet, dass man mindestens eine Verbindung gemäß Anspruch 1 auf die unerwünschten Pflanzen und/oder ihren Lebensraum einwirken lässt.7. A method for controlling undesirable plant growth, characterized in that at least one compound according to claim 1 is allowed to act on the undesired plants and / or their habitat.
8. Verbindungen der allgemeinen Formel (ITf)8. Compounds of the general formula (ITf)
Figure imgf000037_0001
Figure imgf000037_0001
in welcherin which
n, Q, R )3 , R r.4 und X die in Anspruch 1 angegebene Bedeutung haben. n, Q, R) 3, R r.4 and X have the meaning given in claim 1.
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