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WO1996036614A1 - Aminouracil derivates - Google Patents

Aminouracil derivates Download PDF

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Publication number
WO1996036614A1
WO1996036614A1 PCT/EP1996/001819 EP9601819W WO9636614A1 WO 1996036614 A1 WO1996036614 A1 WO 1996036614A1 EP 9601819 W EP9601819 W EP 9601819W WO 9636614 A1 WO9636614 A1 WO 9636614A1
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WO
WIPO (PCT)
Prior art keywords
chlorine
fluorine
optionally substituted
cyano
bromine
Prior art date
Application number
PCT/EP1996/001819
Other languages
German (de)
French (fr)
Inventor
Roland Andree
Mark Wilhelm Drewes
Markus Dollinger
Hans-Joachim Santel
Original Assignee
Bayer Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU58122/96A priority Critical patent/AU5812296A/en
Publication of WO1996036614A1 publication Critical patent/WO1996036614A1/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
    • C07D239/52—Two oxygen atoms
    • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
    • C07D239/545—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals with other 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring

Definitions

  • the invention relates to new aminouracil derivatives, a process for their preparation and their use as herbicides.
  • R 1 represents hydrogen, cyano or halogen
  • R 2 represents cyano, thiocarbamoyl, halogen or optionally substituted alkyl
  • R 3 represents optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl or heterocyclyl,
  • R 4 represents hydrogen, halogen or in each case optionally substituted alkyl or alkoxy and
  • R 5 represents optionally substituted alkyl.
  • R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given above,
  • the new aminouracil derivatives of the general formula (I) are notable for strong herbicidal activity.
  • saturated or unsaturated hydrocarbon chains such as alkyl, alkenyl or alkynyl, are each straight-chain or branched.
  • Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
  • the invention preferably relates to compounds of the formula (I) in which
  • R 1 represents hydrogen, cyano, fluorine, chlorine, bromine or iodine
  • R 2 represents cyano, thiocarbamoyl, fluorine, chlorine, bromine, or alkyl having 1 to 4 carbon atoms which is optionally substituted by fluorine and / or chlorine
  • R 3 is optionally substituted by cyano, fluorine, chlorine, bromine, C r C 4 alkoxy or C] -C 4 -alkylthio-substituted alkyl having 1 to 6 carbon atoms
  • R 3 furthermore represents alkenyl or alkynyl, each with 2 to 6 carbon atoms, optionally substituted by fluorine, chlorine and / or bromine,
  • R 3 furthermore represents cycloalkyl or cycloalkylalkyl with 3 to 8 carbon atoms in the cycloalkyl part and optionally 1 to 4 carbon atoms in the alkyl part, optionally substituted by cyano, fluorine, chlorine, bromine or C 1 -C 4 alkyl,
  • R 3 furthermore for each optionally by fluorine, chlorine, bromine, cyano, nitro, carboxy, carbamoyl, thiocarbamoyl, by C r C 4 alkyl, C r C 4 alkoxy, C r C 4 alkylthio, C r C 4 - Alkylsulf ⁇ nyl or C r C 4 -alkylsulfonyl (which are each optionally substituted by fluorine and / or chlorine), by dimethylaminosulfonyl or diethylaminosulfonyl, by C - C 4 -alkoxy-carbohyl (which is optionally substituted by fluorine, chlorine, bromine,
  • Cyano, methoxy or ethoxy is substituted) by phenyl, phenyloxy or phenylthio (which are each optionally substituted by fluorine, chlorine, bromine, cyano, methyl, methoxy, trifluoromethyl and / or trifluoromethoxy) substituted phenyl, naphthyl, benzyl, phenylethyl , Thienyl, pyrazolyl, pyridinyl or quinolinyl,
  • R 4 represents hydrogen, fluorine, chlorine, bromine or alkyl or alkoxy, each optionally substituted by fluorine and / or chlorine, each having 1 to 4 carbon atoms, and
  • R 5 represents alkyl with 1 to 4 carbon atoms optionally substituted by fluorine and / or chlorine.
  • the invention relates in particular to compounds of the formula (I) in which
  • R 1 represents hydrogen, cyano, fluorine or chlorine
  • R 2 represents cyano, thiocarbamoyl, fluorine, chlorine, bromine, methyl, difluoromethyl or trifluoromethyl
  • R 3 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,
  • R 3 furthermore represents cyclopropyl, cyclobutyl which is optionally substituted by cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl,
  • R 3 for each optionally by fluorine, chlorine, bromine, cyano, nitro, carboxy, carbamoyl, thiocarbamoyl, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy , Trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio,
  • R 4 represents hydrogen, fluorine, chlorine, bromine or methyl, ethyl, n- or i-propyl which is optionally substituted by fluorine and / or chlorine, and
  • R 5 represents methyl, ethyl, n- or i-propyl optionally substituted by fluorine and / or chlorine.
  • the uracil derivatives to be used as starting materials in the process according to the invention for the preparation of the compounds of the formula (I) are generally defined by the formula (II).
  • R 1 , R 2 , R 3 , R 4 and R 5 preferably or in particular have those meanings which have already been mentioned above for
  • the starting materials of the formula (II) are known and / or can be prepared by processes known per se (cf. EP 408382 / US 5084084 / US
  • the process according to the invention is carried out using an electrophilic aminating agent.
  • electrophilic amination agents can be used here. Examples include l-aminooxy-2,4-dinitro-benzene (2,4-dinitro-phenyl-hydroxylamine) and hydroxylamine-O-sulfonic acid.
  • the process according to the invention for the preparation of the compounds of the formula (I) is preferably carried out in the presence of a suitable reaction auxiliary.
  • the usual inorganic or organic bases or acid acceptors are generally suitable as reaction auxiliaries.
  • This preferably includes 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 or calcium carbonate, sodium, potassium or calcium hydrogen carbonate, lithium, sodium, potassium or calcium hydride, lithium, sodium, potassium or calcium hydroxide , Sodium or potassium methanolate, ethanolate, n- or i-propanolate, n-, i-, s- or t-butanolate; also basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyldi
  • the process according to the invention for the preparation of the compounds of the formula (I) is preferably carried out in the presence of a diluent.
  • a diluent is generally suitable as diluents. These preferably include aliphatic, alicyclic and aromatic, optionally halogenated hydrocarbons, such as, for example, pentane, hexane, heptane, petroleum ether, ligroin, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, cyclohexane, methylcyclohexane, dichloromethane (methylene chloride), trichloromethane Chloroform) or carbon tetrachloride, dialkyl ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, ethyl t-butyl ether, methyl t-pentyl
  • Alkanols such as, for example, methanol, ethanol, n- or i-propanol, n-, i-, s- or t-butanol, ethylene glycol monomethyl ether or monoethyl ether, diethyl glycol monomethyl ether or 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 -20 ° C and + 100 ° C, preferably between 0 ° C and 80 ° C, in particular between 20 ° C and 60 ° 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 all plants that grow 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:
  • Matricaria Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronicaex, Abutil Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.
  • Sorghum Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
  • the compounds of the formula (I) are suitable for total weed control, e.g. on industrial and track systems and on
  • the compounds for weed control in permanent crops e.g. 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 and for selective weed control in annual crops.
  • the compounds of formula (I) according to the invention are particularly suitable for the selective control of dicotyledon weeds in monocotyledon crops both in the pre-emergence and in the post-emergence process.
  • 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 Fabrics.
  • formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foaming 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 and 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.
  • alcohols such as butanol or glycol and 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 flours, such as kaolins, clays,
  • Talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, 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, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foaming agents are possible: e.g.
  • nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; suitable dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, 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, for example iron oxide, titanium oxide, ferrocyan blue, and organic dyes, such as alizarin, azo and metal phthalo- cyanine 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 of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention can also be used for weed control in a mixture with known herbicides, finished formulations or tank mixes being possible.
  • herbicides for example anilides, such as e.g. Diflufenican and Propanil; Aryl carboxylic acids, e.g. Dichloropicolinic acid, dicamba and picloram; Aryloxyalkanoic acids, e.g. 2.4 D, 2.4 DB,
  • Aryloxy-phenoxy-alkanoic acid esters e.g. Diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl
  • Azinones e.g. Chloridazon and norflurazon
  • Carbamates e.g. Chlorpropham, desmedipham, phenmedipham and propham
  • Chloroacetanilides e.g.
  • Sethoxydim and tralkoxydim Sethoxydim and tralkoxydim; Imidazolinones, e.g. Imazethapyr, imazamethabenz, imazapyr and imazaquin; Nitriles, e.g. Bromoxynil, dichlobenil and ioxynil; Oxyacetamides, e.g. Mefenacet; Sulfonylureas, e.g.
  • Amidosulfuron bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primi sulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; Thiol carbamates, e.g. Butylates, cycloates, dialallates, EPTC, esprocarb, molinates, prosulfocarb, thiobencarb and triallates; Triazines, e.g.
  • Atrazin cyanazin, simazin, simetryne, terbutryne and terbutylazin; Triazinones, e.g. Hexazinone, metamitron and metribuzin; Others, such as Aminotriazole, benfuresate,
  • active compounds such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.
  • Solutions, suspensions, emulsions, powders, pastes and granules are used. They are used in the usual way, e.g. by pouring, spraying, spraying, sprinkling.
  • the active compounds according to the invention can be applied both before and after the plants emerge. 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.
  • the mixture is diluted to about three times the volume with ethyl acetate.
  • the mixture is then added to approximately the same volume of a saturated aqueous sodium chloride solution, the organic phase is separated off and the aqueous phase is subsequently extracted with ethyl acetate.
  • the combined organic solutions are washed with water, dried with sodium sulfate and filtered. After concentrating the filtrate, the crude product obtained as a residue is purified by column chromatography (silica gel, cyclohexane / ethyl acetate, vol .: 1/1).
  • Solvent 5 parts by weight of acetone 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 watered or sprayed with the active ingredient preparation. The amount of water per unit area is expediently kept constant. The concentration of active substance in the preparation is irrelevant, the only decisive factor is the amount of active substance applied per unit area. After three weeks, the degree of damage to the plants is rated in%
  • the compounds according to Preparation 1, 2 and 3 show very strong activity against weeds such as abutilone (80-100%) with very good tolerance to crop plants, such as maize, (0%) and an application rate of 125 g / ha. ), Amaranthus (80-100%), Galium (90%) and Sinapis (80%).
  • weeds such as abutilone (80-100%) with very good tolerance to crop plants, such as maize, (0%) and an application rate of 125 g / ha. ), Amaranthus (80-100%), Galium (90%) and Sinapis (80%).
  • 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.
  • Test plants which have a height of 5-15 cm are sprayed with the active substance preparation in such a way that the desired amounts of active substance are applied per unit area.
  • the concentration of the spray liquor is chosen so that the desired amounts of active compound are applied in 1000 l of water / ha.
  • the degree of damage to the plants is rated in% damage compared to the development of the untreated control.
  • the compound according to Preparation Example 1 shows good compatibility with crop plants, such as Corn (5%) and one

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The invention relates to novel aminouracil derivatives of general formula (I) in which R?1, R2, R3, R4 and R5¿ have the meanings given in the description, a process for their production and their use as herbicides.

Description

AminouracilderivateAminouracil derivatives
Die Erfindung betrifft neue Aminouracilderivate, ein Verfahren zu ihrer Herstel- lung und ihre Verwendung als Herbizide.The invention relates to new aminouracil derivatives, a process for their preparation and their use as herbicides.
Es ist bekannt, daß bestimmte substituierte Uracile herbizide Eigenschaften auf¬ weisen (vgl. EP 408382/US 5084084/US 5127935/US5154755, EP 563384, DE 4412079). Diese Verbindungen haben jedoch bisher keine nennenswerte Be¬ deutung erlangt.It is known that certain substituted uracils have herbicidal properties (cf. EP 408382 / US 5084084 / US 5127935 / US5154755, EP 563384, DE 4412079). However, these compounds have so far had no significant significance.
Es wurden nun die neuen Aminouracilderivate der allgemeinen Formel (I) ge¬ fundenThe new aminouracil derivatives of the general formula (I) have now been found
Figure imgf000003_0001
in welcher
Figure imgf000003_0001
in which
R1 für Wasserstoff, Cyano oder Halogen steht,R 1 represents hydrogen, cyano or halogen,
R2 für Cyano, Thiocarbamoyl, Halogen oder gegebenenfalls substituiertes Alkyl steht,R 2 represents cyano, thiocarbamoyl, halogen or optionally substituted alkyl,
R3 für jeweils gegebenenfalls substituiertes Alkyl, Alkenyl, Alkinyl, Cyclo- alkyl, Cycloalkylalkyl, Aryl, Arylalkyl oder Heterocyclyl steht,R 3 represents optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl or heterocyclyl,
R4 für Wasserstoff, Halogen oder jeweils gegebenenfalls substituiertes Alkyl oder Alkoxy steht undR 4 represents hydrogen, halogen or in each case optionally substituted alkyl or alkoxy and
R5 für gegebenenfalls substituiertes Alkyl steht. Man erhält die neuen Aminouracilderivate der allgemeinen Formel (I), wenn man Uracilderivate der allgemeinen Formel (II)R 5 represents optionally substituted alkyl. The new aminouracil derivatives of the general formula (I) are obtained if uracil derivatives of the general formula (II)
Figure imgf000004_0001
Figure imgf000004_0001
in welcherin which
R1, R2, R3, R4 und R5 die oben angegebenen Bedeutungen haben,R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given above,
mit einem elektrophilen Aminierungsmittel, gegebenenfalls in Gegenwart eines Re¬ aktionshilfsmittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels um¬ setzt.with an electrophilic aminating agent, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent.
Die neuen Aminouracilderivate der allgemeinen Formel (I) zeichnen sich durch starke herbizide Wirksamkeit aus.The new aminouracil derivatives of the general formula (I) are notable for strong herbicidal activity.
In den Definitionen sind die gesättigten oder ungesättigten Kohlenwasserstoff¬ ketten, wie Alkyl, Alkenyl oder Alkinyl, jeweils geradkettig oder verzweigt.In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkenyl or alkynyl, are each straight-chain or branched.
Halogen steht im allgemeinen für Fluor, Chlor, Brom oder lod, vorzugsweise für Fluor, Chlor oder Brom, insbesondere für Fluor oder Chlor.Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
Gegenstand der Erfindung sind vorzugsweise Verbindungen der Formel (I), in welcherThe invention preferably relates to compounds of the formula (I) in which
R1 für Wasserstoff, Cyano, Fluor, Chlor, Brom oder lod steht,R 1 represents hydrogen, cyano, fluorine, chlorine, bromine or iodine,
R2 für Cyano, Thiocarbamoyl, Fluor, Chlor, Brom, oder für gegebenenfalls durch Fluor und/oder Chlor substituiertes Alkyl mit 1 bis 4 Kohlenstoff- atomen steht, R3 für gegebenenfalls durch Cyano, Fluor, Chlor, Brom, CrC4-Alkoxy oder C]-C4-Alkylthio substituiertes Alkyl mit 1 bis 6 Kohlenstoffatomen steht,R 2 represents cyano, thiocarbamoyl, fluorine, chlorine, bromine, or alkyl having 1 to 4 carbon atoms which is optionally substituted by fluorine and / or chlorine, R 3 is optionally substituted by cyano, fluorine, chlorine, bromine, C r C 4 alkoxy or C] -C 4 -alkylthio-substituted alkyl having 1 to 6 carbon atoms,
R3 weiterhin für jeweils gegebenenfalls durch Fluor, Chlor und/oder Brom substituiertes Alkenyl oder Alkinyl mit jeweils 2 bis 6 Kohlenstoffatomen steht,R 3 furthermore represents alkenyl or alkynyl, each with 2 to 6 carbon atoms, optionally substituted by fluorine, chlorine and / or bromine,
R3 weiterhin für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Brom oder C1-C4-Alkyl substituiertes Cycloalkyl oder Cycloalkylalkyl mit 3 bis 8 Kohlenstoffatomen im Cycloalkylteil und gegebenenfalls 1 bis 4 Kohlen¬ stoffatomen im Alkylteil steht,R 3 furthermore represents cycloalkyl or cycloalkylalkyl with 3 to 8 carbon atoms in the cycloalkyl part and optionally 1 to 4 carbon atoms in the alkyl part, optionally substituted by cyano, fluorine, chlorine, bromine or C 1 -C 4 alkyl,
R3 weiterhin für jeweils gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Nitro, Carboxy, Carbamoyl, Thiocarbamoyl, durch CrC4-Alkyl, CrC4- Alkoxy, CrC4-Alkylthio, CrC4-Alkylsulfιnyl oder CrC4-Alkylsulfonyl (welche jeweils gegebenenfalls durch Fluor und/oder Chlor substituiert sind), durch Dimethylaminosulfonyl oder Diethylaminosulfonyl, durch C - C4-Alkoxy-carbohyl (welches gegebenenfalls durch Fluor, Chlor, Brom,R 3 furthermore for each optionally by fluorine, chlorine, bromine, cyano, nitro, carboxy, carbamoyl, thiocarbamoyl, by C r C 4 alkyl, C r C 4 alkoxy, C r C 4 alkylthio, C r C 4 - Alkylsulfιnyl or C r C 4 -alkylsulfonyl (which are each optionally substituted by fluorine and / or chlorine), by dimethylaminosulfonyl or diethylaminosulfonyl, by C - C 4 -alkoxy-carbohyl (which is optionally substituted by fluorine, chlorine, bromine,
Cyano, Methoxy oder Ethoxy substituiert ist), durch Phenyl, Phenyloxy oder Phenylthio (welche jeweils gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Methyl, Methoxy, Trifluormethyl und/oder Trifluormethoxy sub¬ stituiert sind) substituiertes Phenyl, Naphthyl, Benzyl, Phenylethyl, Thienyl, Pyrazolyl, Pyridinyl oder Chinolinyl steht,Cyano, methoxy or ethoxy is substituted) by phenyl, phenyloxy or phenylthio (which are each optionally substituted by fluorine, chlorine, bromine, cyano, methyl, methoxy, trifluoromethyl and / or trifluoromethoxy) substituted phenyl, naphthyl, benzyl, phenylethyl , Thienyl, pyrazolyl, pyridinyl or quinolinyl,
R4 für Wasserstoff, Fluor, Chlor, Brom oder für jeweils gegebenenfalls durch Fluor und/oder Chlor substituiertes Alkyl oder Alkoxy mit jeweils 1 bis 4 Kohlenstoffatomen steht, undR 4 represents hydrogen, fluorine, chlorine, bromine or alkyl or alkoxy, each optionally substituted by fluorine and / or chlorine, each having 1 to 4 carbon atoms, and
R5 für gegebenenfalls durch Fluor und/oder Chlor substituiertes Alkyl mit 1 bis 4 Kohlenstoffatomen steht.R 5 represents alkyl with 1 to 4 carbon atoms optionally substituted by fluorine and / or chlorine.
Die Erfindung betrifft insbesondere Verbindungen der Formel (I), in welcherThe invention relates in particular to compounds of the formula (I) in which
R1 für Wasserstoff, Cyano, Fluor oder Chlor steht,R 1 represents hydrogen, cyano, fluorine or chlorine,
R2 für Cyano, Thiocarbamoyl, Fluor, Chlor, Brom, Methyl, Difluormethyl oder Trifluormethyl steht, R3 für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl steht,R 2 represents cyano, thiocarbamoyl, fluorine, chlorine, bromine, methyl, difluoromethyl or trifluoromethyl, R 3 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,
R3 weiterhin für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Brom, Methyl, Ethyl, n- oder i-Propyl substituiertes Cyclopropyl, Cyclobutyl,R 3 furthermore represents cyclopropyl, cyclobutyl which is optionally substituted by cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl,
Cyclopentyl oder Cyclohexyl steht,Cyclopentyl or cyclohexyl,
R3 weiterhin für jeweils gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Nitro, Carboxy, Carbamoyl, Thiocarbamoyl, Methyl, Ethyl, n- oder i- Propyl, Trifluormethyl, Methoxy, Ethoxy, n- oder i-Propoxy, Difluor- methoxy, Trifluormethoxy, Methylthio, Ethylthio, n- oder i-Propylthio,R 3 for each optionally by fluorine, chlorine, bromine, cyano, nitro, carboxy, carbamoyl, thiocarbamoyl, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy , Trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio,
Methylsulfinyl, Ethylsulfinyl, n- oder i-Propyl sulfinyl, Methylsulfonyl, Ethylsulfonyl, n- oder i-Propylsulfonyl, Dimethylaminosulfonyl, Diethyl- aminosulfonyl, Methoxycarbonyl, Ethoxycarbonyl, n- oder i-Propoxy- carbonyl substituiertes Phenyl, Naphthyl, Benzyl, Thienyl, Pyrazolyl oder Pyridinyl steht,Methylsulfinyl, ethylsulfinyl, n- or i-propyl sulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, dimethylaminosulfonyl, diethylaminosulfonyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl substituted phenyl, naphthyl, benzyl, benzyl, Pyrazolyl or pyridinyl,
R4 für Wasserstoff, Fluor, Chlor, Brom oder für jeweils gegebenenfalls durch Fluor und/oder Chlor substituiertes Methyl, Ethyl, n- oder i-Propyl steht, undR 4 represents hydrogen, fluorine, chlorine, bromine or methyl, ethyl, n- or i-propyl which is optionally substituted by fluorine and / or chlorine, and
R5 für gegebenenfalls durch Fluor und/oder Chlor substituiertes Methyl, Ethyl, n- oder i-Propyl steht.R 5 represents methyl, ethyl, n- or i-propyl optionally substituted by fluorine and / or chlorine.
Die oben aufgeführten allgemeinen oder in Vorzugsbereichen aufgeführten Reste¬ definitionen gelten sowohl für die Endprodukte der Formel (I), als auch ent¬ sprechend für die jeweils zur Herstellung benötigten Ausgangsstoffe bzw. Zwischenprodukte. Diese Restedefinitionen können untereinander, also auch zwi- sehen den angegebenen bevorzugten Bereichen beliebig kombiniert werden.The general or preferred radical definitions listed above apply both to the end products of the formula (I) and correspondingly to the starting materials or intermediates required in each case for the preparation. These residual definitions can be combined with one another, that is to say also between the specified preferred ranges.
Verwendet man beispielsweise l-(4-Chlor-2-fluor-5-methylsulfonylamino-phenyl)- 3,6-dihydro-2,6-dioxo-4-methyl-l(2H)-pyrimidin als Ausgangsstoff und 1-Amino- oxy-2,4-dinitro-benzol als elektrophiles Aminierungsmittel, so kann der Reaktions¬ ablauf beim erfindungsgemäßen Verfahren durch das folgende Formelschema skizziert werden:
Figure imgf000007_0001
For example, if 1- (4-chloro-2-fluoro-5-methylsulfonylamino-phenyl) -3,6-dihydro-2,6-dioxo-4-methyl-1 (2H) -pyrimidine is used as the starting material and 1-amino- oxy-2,4-dinitro-benzene as an electrophilic aminating agent, the course of the reaction in the process according to the invention can be outlined using the following formula:
Figure imgf000007_0001
Die beim erfindungsgemäßen Verfahren zur Herstellung der Verbindungen der Formel (I) als Ausgangsstoffe zu verwendenden Uracilderivate sind durch die Formel (II) allgemein definiert. In der Formel (II) haben R1, R2, R3, R4 und R5 vorzugsweise bzw. insbesondere diejenigen Bedeutungen, die bereits oben bei derThe uracil derivatives to be used as starting materials in the process according to the invention for the preparation of the compounds of the formula (I) are generally defined by the formula (II). In the formula (II), R 1 , R 2 , R 3 , R 4 and R 5 preferably or in particular have those meanings which have already been mentioned above for
Beschreibung der erfindungsgemäß herzustellenden Verbindungen der Formel (I) vorzugsweise bzw. als insbesondere bevorzugt für R1, R2, R3, R4 und R5 ange¬ geben wurden.Description of the compounds of the formula (I) to be prepared according to the invention have been given preferably or as particularly preferred for R 1 , R 2 , R 3 , R 4 and R 5 .
Die Ausgangsstoffe der Formel (II) sind bekannt und/oder können nach an sich be- kannten Verfahren hergestellt werden (vgl. EP 408382/US 5084084/USThe starting materials of the formula (II) are known and / or can be prepared by processes known per se (cf. EP 408382 / US 5084084 / US
5127935/US5154755, EP 563384, DE 4412079).5127935 / US5154755, EP 563384, DE 4412079).
Das erfindungsgemäße Verfahren wird unter Verwendung eines elektrophilen Aminierungsmittels durchgeführt. Es können hierbei die üblichen elektrophilen Amini erungsmittel eingesetzt werden. Als Beispiele hierfür seien l-Aminooxy-2,4- dinitro-benzol (2,4-Dinitro-phenyl-hydroxylamin) und Hydroxylamin-O-sulfonsäure genannt.The process according to the invention is carried out using an electrophilic aminating agent. The usual electrophilic amination agents can be used here. Examples include l-aminooxy-2,4-dinitro-benzene (2,4-dinitro-phenyl-hydroxylamine) and hydroxylamine-O-sulfonic acid.
Das erfindungsgemäße Verfahren zur Herstellung der Verbindungen der Formel (I) wird vorzugsweise in Gegenwart eines geeigneten Reaktionshilfsmittels durchge¬ führt. Als Reaktionshilfsmittel kommen im allgemeinen die üblichen an- organischen oder organischen Basen oder Säureakzeptoren in Betracht. Hierzu ge¬ hören vorzugsweise Alkalimetall- oder Erdalkalimetall- -acetate, -amide, -carbonate, -hydrogencarbonate, -hydride, -hydroxide oder -alkanolate, wie bei¬ spielsweise Natrium-, Kalium- oder Calcium-acetat, Lithium-, Natrium-, Kalium- oder Calcium-amid, Natrium-, Kalium- 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-, i-, s- oder t-butanolat; weiterhin auch basische organische Stickstoffverbindungen, wie beispielsweise Tri- methylamin, Triethylamin, Tripropylamin, Tributylamin, Ethyl-diisopropylamin, N,N-Dimethyl-cyclohexylamin, Dicyclohexylamin, Ethyl-dicyclohexylamin, N,N- Dimethyl-anilin, N,N-Dimethyl-benzylamin, Pyridin, 2-Methyl-, 3-Methyl-, 4- Methyl-, 2,4-Dimethyl-, 2,6-Dimethyl-, 3,4-Dimethyl- und 3,5-Dimethyl-pyridin, 5- Ethyl-2-methyl-pyridin, 4-Dimethylamino-pyridin, N-Methyl-piperidin, 1,4-Diaza- bicyclo[2,2,2]-octan (DABCO), l,5-Diazabicyclo[4,3,0]-non-5-en (DBN), und 1 ,8-Diazabicyclo[5,4,0]-undec-7-en (DBU).The process according to the invention for the preparation of the compounds of the formula (I) is preferably carried out in the presence of a suitable reaction auxiliary. The usual inorganic or organic bases or acid acceptors are generally suitable as reaction auxiliaries. This preferably includes 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 or calcium carbonate, sodium, potassium or calcium hydrogen carbonate, lithium, sodium, potassium or calcium hydride, lithium, sodium, potassium or calcium hydroxide , Sodium or potassium methanolate, ethanolate, n- or i-propanolate, n-, i-, s- or t-butanolate; also basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyldiisopropylamine, N, N-dimethylcyclohexylamine, dicyclohexylamine, ethyldicyclohexylamine, N, N-dimethylaniline, N, N-dimethyl benzylamine, pyridine, 2-methyl, 3-methyl, 4-methyl, 2,4-dimethyl, 2,6-dimethyl, 3,4-dimethyl and 3,5-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), and 1,8-diazabicyclo [5,4,0] -undec-7-ene (DBU).
Das erfindungsgemäße Verfahren zur Herstellung der Verbindungen der Formel (I) wird vorzugsweise in Gegenwart eines Verdünnungsmittels durchgeführt. Als Ver- dünnungsmittel kommen im allgemeinen die üblichen organischen Lösungsmittel in Betracht. Hierzu gehören vorzugsweise aliphatische, alicyclische und aroma¬ tische, gegebenenfalls halogenierte Kohlenwasserstoffe, wie beispielsweise Pentan, Hexan, Heptan, Petrolether, Ligroin, Benzin, Benzol, Toluol, Xylol, Chlorbenzol, Dichlorbenzol, Cyclohexan, Methylcyclohexan, Dichlormethan (Methylenchlorid), Trichlormethan (Chloroform) oder Tetrachlormethan, Dialkylether, wie beispiels¬ weise Diethylether, Diisopropylether, Methyl -t-butylether, Ethyl -t-buty lether, Methyl-t-pentylether (MTBE), Ethyl-t-pentylether, Tetrahydrofuran (THF), 1,4- Dioxan, Ethylenglycol-dimethylether oder -diethylether, Diethylenglycol-dimethyl- ether oder -diethylether; Dialkylketone, wie beispielsweise Aceton, Butanon (Methylethylketon), Methyl-i-propylketon oder Methyl-i-butylketon, Nitrile, wie beispielsweise Acetonitril, Propionitril, Butyronitril oder Benzonitril; Amide, wie beispielsweise N,N-Dimethyl-formamid (DMF), N,N-Dimethyl-acetamid, N-Methyl-formanilid, N-Methyl-pyrrolidon oder Hexamethyl-phosphorsäuretriamid; Ester, wie beispielsweise Essigsäure-methylester, -ethylester, -n- oder -i-propyl- ester, -n-, -i- oder -s-butylester; Sulfoxide, wie beispielsweise Dimethylsulfoxid;The process according to the invention for the preparation of the compounds of the formula (I) is preferably carried out in the presence of a diluent. The usual organic solvents are generally suitable as diluents. These preferably include aliphatic, alicyclic and aromatic, optionally halogenated hydrocarbons, such as, for example, pentane, hexane, heptane, petroleum ether, ligroin, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, cyclohexane, methylcyclohexane, dichloromethane (methylene chloride), trichloromethane Chloroform) or carbon tetrachloride, dialkyl ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, ethyl t-butyl ether, methyl t-pentyl ether (MTBE), ethyl t-pentyl ether, tetrahydrofuran (THF), 1, 4- dioxane, ethylene glycol dimethyl ether or diethyl ether, diethylene glycol dimethyl ether or diethyl ether; Dialkyl ketones, such as, for example, acetone, butanone (methyl ethyl ketone), methyl i-propyl ketone or methyl i-butyl ketone, nitriles, such as, for example, acetonitrile, propionitrile, butyronitrile or benzonitrile; Amides, such as, for example, N, N-dimethylformamide (DMF), N, N-dimethyl-acetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethyl-phosphoric acid triamide; Esters, such as, for example, methyl acetate, ethyl ester, n- or i-propyl ester, n-, i- or s-butyl ester; Sulfoxides such as dimethyl sulfoxide;
Alkanole, wie beispielsweise Methanol, Ethanol, n- oder i-Propanol, n-, i-, s- oder t-Butanol, Ethylenglycol-monomethylether oder -monoethy lether, Di ethyl englycol - monom ethyl ether oder -monoethy lether; 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 -20°C und +100°C, vorzugsweise zwischen 0°C und 80°C, insbesondere zwischen 20°C und 60°C.Alkanols, such as, for example, methanol, ethanol, n- or i-propanol, n-, i-, s- or t-butanol, ethylene glycol monomethyl ether or monoethyl ether, diethyl glycol monomethyl ether or 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 -20 ° C and + 100 ° C, preferably between 0 ° C and 80 ° C, in particular between 20 ° C and 60 ° C.
Das erfindungsgemäße Verfahren wird im allgemeinen unter Normaldruck durch¬ geführt. 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 Her¬ stellungsbeispiele).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, Krautab- tötungsmittel 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 all plants that grow 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: Sinapis, Lepidium, Galium, Stellaria,Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,
Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum. Dikotyle Kulturen der Gattungen: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronicaex, Abutil Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum. Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.
Monokotyle Unkräuter der Gattungen: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus,Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus,
Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
Monokotyle Kulturen der Gattungen: Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.
Die Verwendung der erfindungsgemäßen Wirkstoffe ist jedoch keineswegs auf diese Gattungen beschränkt, sondern erstreckt sich in gleicher Weise auch auf andere Pflanzen.However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants.
Die Verbindungen der Formel (I) eignen sich in Abhängigkeit von der Konzen- tration zur Totalunkrautbekämpfung z.B. auf Industrie- und Gleisanlagen und aufDepending on the concentration, the compounds of the formula (I) are suitable for total weed control, e.g. on industrial and track systems and on
Wegen und Plätzen mit und ohne Baumbewuchs. Ebenso können die Verbin¬ dungen zur Unkrautbekämpfung in Dauerkulturen, z.B. Forst, Ziergehölz-, Obst-, Wein-, Citrus-, Nuß-, Bananen-, Kaffee-, Tee-, Gummi-, Ölpalm-, Kakao-, Beeren¬ frucht- und Hopfenanlagen, auf Zier- und Sportrasen und Weideflächen und zur selektiven Unkrautbekämpfung in einjährigen Kulturen eingesetzt werden.Because of and places with and without tree cover. Likewise, the compounds for weed control in permanent crops, e.g. 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 and for selective weed control in annual crops.
Die erfindungsgemäßen Verbindungen der Formel (I) eignen sich insbesondere zur selektiven Bekämpfung von dikotylen Unkräutern in monokotylen Kulturen sowohl im Vorauflauf- als auch im Nachauflauf- Verfahren.The compounds of formula (I) according to the invention are particularly suitable for the selective control of dicotyledon weeds in monocotyledon crops both in the pre-emergence and in the post-emergence process.
Die Wirkstoffe können in die üblichen Formulierungen übergeführt werden, wie Lösungen, Emulsionen, Spritzpulver, Suspensionen, Pulver, Stäubemittel, Pasten, lösliche Pulver, Granulate, Suspensions-Emulsions-Konzentrate, Wirkstoff-impräg¬ nierte 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 Fabrics.
Diese Formulierungen werden in bekannter Weise hergestellt, z.B. durch Ver- mischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumer¬ zeugenden Mitteln.These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foaming 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 Kohlen¬ wasserstoffe, 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 Cyclo- hexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethyl- sulfoxid, 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 and 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 Gesteinsmehle, wie Kaoline, Tonerden,Possible solid carriers are: e.g. Ammonium salts and natural rock flours, such as kaolins, clays,
Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate, als feste Trägerstoffe für Granulate kommen in Frage: z.B. gebrochene und fraktionierte natürliche Gesteine wie Calcit, 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 Emulgatoren, wie Polyoxyethylen-Fett- säure-Ester, Polyoxyethylen-Fettalkohol-Ether, z.B. Alkylarylpolyglykol ether, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Disper¬ giermittel kommen in Frage: z.B. Lignin-Sulfitablaugen und Methylcellulose.Talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, 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, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foaming agents are possible: e.g. nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; suitable dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.
Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natürliche und synthetische pulvrige, körnige oder latexförmige Polymere ver¬ wendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospholipide, wie Kephaline und Lecithine und synthetische Phospho- lipide. Weitere Additive können mineralische und vegetabile Öle sein.Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, 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, Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo- und Metallphthalo- cyanin-farbstoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden.Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue, and organic dyes, such as alizarin, azo and metal phthalo- cyanine 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 Gewichts¬ prozent Wirkstoff, vorzugsweise zwischen 0,5 und 90 %.The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
Die erfindungsgemäßen Wirkstoffe können als solche oder in ihren Formulie¬ rungen auch in Mischung mit bekannten Herbiziden zur Unkrautbekämpfung Ver¬ wendung finden, wobei Fertigformulierungen oder Tankmischungen möglich sind.The active compounds according to the invention, as such or in their formulations, can also be used for weed control in a mixture with known herbicides, finished formulations or tank mixes being possible.
Für die Mischungen kommen bekannte Herbizide infrage, beispielsweise Anilide, wie z.B. Diflufenican und Propanil; Arylcarbonsäuren, wie z.B. Dichlorpicolin- säure, Dicamba und Picloram; Aryloxyalkansäuren, wie z.B. 2,4 D, 2,4 DB,Known herbicides, for example anilides, such as e.g. Diflufenican and Propanil; Aryl carboxylic acids, e.g. Dichloropicolinic acid, dicamba and picloram; Aryloxyalkanoic acids, e.g. 2.4 D, 2.4 DB,
2,4 DP, Fluroxypyr, MCPA, MCPP und Triclopyr; Aryloxy-phenoxy-alkansäure- ester, wie z.B. Diclofop-methyl, Fenoxaprop-ethyl, Fluazifop-butyl, Haloxyfop- methyl und Quizalofop-ethyl; Azinone, wie z.B. Chloridazon und Norflurazon; Carbamate, wie z.B. Chlorpropham, Desmedipham, Phenmedipham und Propham; Chloracetanilide, wie z.B. Alachlor, Acetochlor, Butachlor, Metazachlor, Metola- chlor, Pretilachlor und Propachlor; Dinitroaniline, wie z.B. Oryzalin, Pendimethalin und Trifluralin; Diphenylether, wie z.B. Acifluorfen, Bifenox, Fluoroglycofen, Fomesafen, Halosafen, Lactofen und Oxyfluorfen; Harnstoffe, wie z.B. Chlortoluron, Diuron, Fluometuron, Isoproturon, Linuron und Methabenz- thiazuron; Hydroxylamine, wie z.B. Alloxydim, Clethodim, Cycloxydim,2.4 DP, fluroxypyr, MCPA, MCPP and triclopyr; Aryloxy-phenoxy-alkanoic acid esters, e.g. Diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; Azinones, e.g. Chloridazon and norflurazon; Carbamates, e.g. Chlorpropham, desmedipham, phenmedipham and propham; Chloroacetanilides, e.g. Alachlor, acetochlor, butachlor, metazachlor, metolochlor, pretilachlor and propachlor; Dinitroanilines, e.g. Oryzalin, pendimethalin and trifluralin; Diphenyl ethers, e.g. Acifluorfen, Bifenox, Fluoroglycofen, Fomesafen, Halosafen, Lactofen and Oxyfluorfen; Ureas, e.g. Chlorotoluron, diuron, fluometuron, isoproturon, linuron and methabenzthiazuron; Hydroxylamines, e.g. Alloxydim, clethodim, cycloxydim,
Sethoxydim und Tralkoxydim; Imidazolinone, wie z.B . Imazethapyr, Imazamethabenz, Imazapyr und Imazaquin; Nitrile, wie z.B. Bromoxynil, Dichlobenil und Ioxynil; Oxyacetamide, wie z.B. Mefenacet; Sulfonylharnstoffe, wie z.B. Amidosulfuron, Bensulfuron-methyl, Chlorimuron-ethyl, Chlorsulfuron, Cinosulfuron, Metsulfuron-methyl, Nicosulfuron, Primi sulfuron, Pyrazosulfuron- ethyl, Thifensulfuron-methyl, Triasulfuron und Tribenuron-methyl; Thiolcarbamate, wie z.B. Butylate, Cycloate, Diallate, EPTC, Esprocarb, Molinate, Prosulfocarb, Thiobencarb und Triallate; Triazine, wie z.B. Atrazin, Cyanazin, Simazin, Simetryne, Terbutryne und Terbutylazin; Triazinone, wie z.B. Hexazinon, Metamitron und Metribuzin; Sonstige, wie z.B. Aminotriazol, Benfuresate,Sethoxydim and tralkoxydim; Imidazolinones, e.g. Imazethapyr, imazamethabenz, imazapyr and imazaquin; Nitriles, e.g. Bromoxynil, dichlobenil and ioxynil; Oxyacetamides, e.g. Mefenacet; Sulfonylureas, e.g. Amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primi sulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; Thiol carbamates, e.g. Butylates, cycloates, dialallates, EPTC, esprocarb, molinates, prosulfocarb, thiobencarb and triallates; Triazines, e.g. Atrazin, cyanazin, simazin, simetryne, terbutryne and terbutylazin; Triazinones, e.g. Hexazinone, metamitron and metribuzin; Others, such as Aminotriazole, benfuresate,
Bentazone, Cinmethylin, Clomazone, Clopyralid, Difenzoquat, Dithiopyr, Ethofumesate, Fluorochloridone, Glufosinate, Glyphosate, Isoxaben, Pyridate, Quinchlorac, Quinmerac, Sulphosate und Tridiphane. Auch eine Mischung mit anderen bekannten Wirkstoffen, wie Fungiziden, Insektiziden, Akariziden, Nematiziden, Schutzstoffen gegen Vogelfraß, Pflanzen¬ nährstoffen und Bodenstruktur-verbesserungsmitteln ist möglich.Bentazone, Cinmethylin, Clomazone, Clopyralid, Difenzoquat, Dithiopyr, Ethofumesate, Fluorochloridone, Glufosinate, Glyphosate, Isoxaben, Pyridate, Quinchlorac, Quinmerac, Sulphosate and Tridiphane. 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 gebrauchsfertigeThe active ingredients as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use
Lösungen, Suspensionen, Emulsionen, Pulver, Pasten und Granulate angewandt werden. Die Anwendung geschieht in üblicher Weise, z.B. durch Gießen, Spritzen, Sprühen, Streuen.Solutions, suspensions, emulsions, powders, pastes and granules are used. They are used in the usual way, e.g. by pouring, spraying, spraying, sprinkling.
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.The active compounds according to the invention can be applied both before and after the plants emerge. 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 Boden- fläche, 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.
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.
HersteHungsbeispiele:MANUFACTURING EXAMPLES:
Beispiel 1example 1
Figure imgf000014_0001
Figure imgf000014_0001
2,1 g (5 mMol) l-(4-Cyano-2-fluor-5-ethylsulfonylamino-phenyl)-3,6-dihydro-2,6- dioxo-4-trifluormethyl-l(2H)-pyrimidin werden in 20 ml N,N-Dimethyl-formamid vorgelegt und 0,5 g (20 mMol) Natriumhydrid werden dazu gegeben. Die Mischung wird 15 Minuten bei Raumtemperatur (ca. 20°C) gerührt. Anschließend wird 1 g (5 mMol) l-Aminooxy-2,4-dinitro-benzol (2,4-Dinitro-phenyl-hydroxyl- amin) dazu gegeben und die Mischung wird ca. 30 Minuten bei ca. 20°C gerührt. Dann wird noch einmal 1 g und nach weiteren 30 Minuten Rühren noch weitere 0,5 g l-Aminooxy-2,4-dinitro-benzol zur Mischung gegeben, wonach weitere 4 Stunden bei ca. 20°C gerührt wird. Zur Aufarbeitung wird mit Essigsäureethylester auf etwa das etwa das dreifache Volumen verdünnt. Die Mischung wird dann auf etwa das gleiche Volumen einer gesättigten wässrigen Kochsalzlösung gegeben, die organische Phase abgetrennt und die wässrige Phase mit Essigsäureethylester nachextrahiert. Die vereinigten organischen Lösungen werden mit Wasser ge¬ waschen, mit Natriumsulfat getrocknet und filtriert. Nach Einengen des Filtrats wird das als Rückstand erhaltene Rohprodukt durch Säulenchromatographie (Kieselgel, Cyclohexan/Essigsäureethylester, Vol.: 1/1) gereinigt.2.1 g (5 mmol) of l- (4-cyano-2-fluoro-5-ethylsulfonylaminophenyl) -3,6-dihydro-2,6-dioxo-4-trifluoromethyl-l (2H) -pyrimidine are in 20 ml of N, N-dimethylformamide and 0.5 g (20 mmol) of sodium hydride are added. The mixture is stirred for 15 minutes at room temperature (approx. 20 ° C). Then 1 g (5 mmol) of l-aminooxy-2,4-dinitro-benzene (2,4-dinitro-phenyl-hydroxylamine) is added and the mixture is stirred at about 20 ° C. for about 30 minutes. Then another 1 g and, after stirring for a further 30 minutes, another 0.5 g of l-aminooxy-2,4-dinitro-benzene are added to the mixture, after which the mixture is stirred for a further 4 hours at approx. For working up, the mixture is diluted to about three times the volume with ethyl acetate. The mixture is then added to approximately the same volume of a saturated aqueous sodium chloride solution, the organic phase is separated off and the aqueous phase is subsequently extracted with ethyl acetate. The combined organic solutions are washed with water, dried with sodium sulfate and filtered. After concentrating the filtrate, the crude product obtained as a residue is purified by column chromatography (silica gel, cyclohexane / ethyl acetate, vol .: 1/1).
Man erhält 0,25 g (11% der Theorie) 3-Amino-l-[4-Cyano-2-fluor-5-(l-ethyl- sulfonyl-hydrazino)-phenyl]-3,6-dihydro-2,6-dioxo-4-trifluormethyl-l(2H)-pyrimi- din vom Schmelzpunkt 267°C.0.25 g (11% of theory) of 3-amino-l- [4-cyano-2-fluoro-5- (l-ethylsulfonylhydrazino) phenyl] -3,6-dihydro-2 are obtained, 6-dioxo-4-trifluoromethyl-1 (2H) -pyrimidine with melting point 267 ° C.
Analog Beispiel 1 sowie entsprechend der allgemeinen Beschreibung des erfin¬ dungsgemäßen Herstellungsverfahrens können beispielsweise auch die in der nach- stehenden Tabelle 1 aufgeführten Verbindungen der Formel (I) hergestellt werden.
Figure imgf000015_0001
Analogously to Example 1 and in accordance with the general description of the production 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 imgf000015_0001
Tabelle 1 : Beispiele für die Verbindungen der Formel (I)Table 1: Examples of the compounds of the formula (I)
Bsp. R1 R R3 R4 R5 Schmelz¬Example R 1 RR 3 R 4 R 5 Schmelz¬
Nr. punkt (°C)No. point (° C)
2 F CN n-C3H7 H CF3 2002 F CN nC 3 H 7 H CF 3 200
3 F CN i-C3H7 H CF3 2753 F CN iC 3 H 7 H CF 3 275
4 F CN CH3 H CF3 4 F CN CH 3 H CF 3
5 F CN CH3 CH3 CF3 5 F CN CH 3 CH 3 CF 3
6 F CN C2H5 Cl CF3 6 F CN C 2 H 5 Cl CF 3
7 F CN CH3 H CHF2 7 F CN CH 3 H CHF 2
8 F CN n-C4H9 H CHF2 8 F CN nC 4 H 9 H CHF 2
9 F CN n-C3H7 H CHF2 9 F CN nC 3 H 7 H CHF 2
10 F s CH, H CF,10 F s CH, H CF,
NH„NH "
11 H CN n-C3H7 Cl CF3 11 H CN nC 3 H 7 Cl CF 3
12 H CN C2H5 H CF2C1 (Fortsetzung Tabelle 1)12 H CN C 2 H 5 H CF 2 C1 (Continued in Table 1)
Bsp. R1 R^ Rά R4 R5 Schmelz-Example R 1 R ^ R ά R 4 R 5 melting
Nr. punkt (°C)No. point (° C)
13 F CN C2H5 H CF2CF3 14 F S CH, H CHF-,13 F CN C 2 H 5 H CF 2 CF 3 14 FS CH, H CHF-,
NH,NH,
Figure imgf000016_0001
Figure imgf000016_0001
16 F CN CH3 H CF2C116 F CN CH 3 H CF 2 C1
17 F s CH3 H CF2C117 F s CH 3 H CF 2 C1
^NH2 ^ NH 2
18 F CN C2H5 H CHF2 18 F CN C 2 H 5 H CHF 2
19 F s C2H5 H CF2CF; 19 F s C 2 H 5 H CF 2 CF ;
^NH2 ^ NH 2
20 F CN C2H5 CH3 CF2CF-20 F CN C 2 H 5 CH 3 CF 2 CF-
21 F s CH3 CH3 CF3 21 F s CH 3 CH 3 CF 3
^NH2 ^ NH 2
22 F CN C2H5 Cl CF2C122 F CN C 2 H 5 Cl CF 2 C1
23 F S CH3 H CF2C1 -^NH2 23 FS CH 3 H CF 2 C1 - ^ NH 2
24 F CN C2H5 Cl CF3 24 F CN C 2 H 5 Cl CF 3
25 F CN n-C5Hπ H CF3 25 F CN nC 5 H π H CF 3
26 F Cl C2H5 H CF3 26 F Cl C 2 H 5 H CF 3
27 Cl Cl C2H5 H CF3 27 Cl Cl C 2 H 5 H CF 3
28 F Br C2H5 H CF3 28 F Br C 2 H 5 H CF 3
29 F Cl C2H5 CH3 CF3 29 F Cl C 2 H 5 CH 3 CF 3
30 F Cl CH3 H CF3 30 F Cl CH 3 H CF 3
31 F CN -CH2CH CH2C1 H CF3 Anwendungsbeispiele:31 F CN -CH 2 CH CH 2 C1 H CF 3 Examples of use:
Beispiel AExample A
Pre-emergence-TestPre-emergence test
Lösungsmittel: 5 Gewichtsteile Aceton Emulgator: 1 Gewichtsteil AlkylarylpolyglykoletherSolvent: 5 parts by weight of acetone emulsifier: 1 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Ge¬ wichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel, gibt die ange¬ gebene Menge Emulgator zu und verdünnt das Konzentrat mit Wasser auf die ge¬ wünschte Konzentration. Samen der Testpflanzen werden in normalen Boden ausgesät. Der Boden wird nach 24 Stunden mit der Wirkstoffzubereitung begossen bzw. gespritzt. Dabei hält man die Wassermenge pro Flächeneinheit zweckmäßigerweise konstant. Die Wirk- stoffkonzentration in der Zubereitung spielt keine Rolle, entscheidend ist nur die Aufwandmenge des Wirkstoffs pro Flächeneinheit. Nach drei Wochen wird der Schädigungsgrad der Pflanzen bonitiert in %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. Seeds of the test plants are sown in normal soil. After 24 hours, the soil is watered or sprayed with the active ingredient preparation. The amount of water per unit area is expediently kept constant. The concentration of active substance in the preparation is irrelevant, the only decisive factor is the amount of active substance applied per unit area. After three weeks, the degree of damage to the plants is rated in%
Schädigung im Vergleich zur Entwicklung der unbehandelten Kontrolle.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 Herstellungs¬ beispiel 1, 2 und 3 bei sehr guter Verträglichkeit gegenüber Kulturpflanzen, wie z.B. Mais, (0%) und einer Aufwandmenge von 125g/ha sehr starke Wirkung gegen Unkräuter wie Abutilon (80-100%), Amaranthus (80-100%), Galium (90%) und Sinapis (80%). B ei spiel BIn this test, for example, the compounds according to Preparation 1, 2 and 3 show very strong activity against weeds such as abutilone (80-100%) with very good tolerance to crop plants, such as maize, (0%) and an application rate of 125 g / ha. ), Amaranthus (80-100%), Galium (90%) and Sinapis (80%). 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 Ge¬ wichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel, gibt die ange¬ gebene Menge Emulgator zu und verdünnt das Konzentrat mit Wasser auf die ge¬ wünschte 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.
Mit der Wirkstoffzubereitung spritzt man Testpflanzen, welche eine Höhe von 5 -15 cm haben so, daß die jeweils gewünschten Wirkstoffmengen pro Flächen¬ einheit ausgebracht werden. Die Konzentration der Spritzbrühe wird so gewählt, daß in 1000 1 Wasser/ha die jeweils gewünschten Wirkstoffmengen ausgebracht werden.Test plants which have a height of 5-15 cm are sprayed with the active substance preparation in such a way that the desired amounts of active substance are applied per unit area. The concentration of the spray liquor is chosen so that the desired amounts of active compound are applied in 1000 l of water / ha.
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 zeigt beispielsweise die Verbindung gemäß Herstellungsbeispiel 1 bei guter Verträglichkeit gegenüber Kulturpflanzen, wie z.B. Mais (5%) und einerIn this test, for example, the compound according to Preparation Example 1 shows good compatibility with crop plants, such as Corn (5%) and one
Aufwandmenge von nur 30g/ha sehr starke Wirkung gegen Unkräuter wie Abutilon (100%), Amaranthus (100%), Galium (100%) und Sinapis (100%). Application rate of only 30g / ha very strong action against weeds such as Abutilon (100%), Amaranthus (100%), Galium (100%) and Sinapis (100%).

Claims

Patentansprüche claims
1. Aminouracilderivate der allgemeinen Formel (I)1. Aminouracil derivatives of the general formula (I)
Figure imgf000019_0001
Figure imgf000019_0001
in welcherin which
R1 für Wasserstoff, Cyano oder Halogen steht,R 1 represents hydrogen, cyano or halogen,
R2 für Cyano, Thiocarbamoyl, Halogen oder gegebenenfalls substitu¬ iertes Alkyl steht,R 2 represents cyano, thiocarbamoyl, halogen or optionally substituted alkyl,
R3 für jeweils gegebenenfalls substituiertes Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cycloalkylalkyl, Aryl, Arylalkyl oder Heterocyclyl steht,R 3 represents in each case optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl or heterocyclyl,
R4 für Wasserstoff, Halogen oder jeweils gegebenenfalls substituiertes Alkyl oder Alkoxy steht undR 4 represents hydrogen, halogen or in each case optionally substituted alkyl or alkoxy and
R5 für gegebenenfalls substituiertes Alkyl steht.R 5 represents optionally substituted alkyl.
2. Aminouracilderivate der allgemeinen Formel (I) gemäß Anspruch 1, dadurch gekennzeichnet, daß2. Aminouracil derivatives of the general formula (I) according to claim 1, characterized in that
R1 für Wasserstoff, Cyano, Fluor, Chlor, Brom oder lod steht,R 1 represents hydrogen, cyano, fluorine, chlorine, bromine or iodine,
R2 für Cyano, Thiocarbamoyl, Fluor, Chlor, Brom, oder für gegebenen¬ falls durch Fluor und/oder Chlor substituiertes Alkyl mit 1 bis 4 Kohlenstoffatomen steht, R3 für gegebenenfalls durch Cyano, Fluor, Chlor, Brom, 0,-04- Alkoxy oder C]-C4-Alkylthio substituiertes Alkyl mit 1 bis 6 Kohlenstoff¬ atomen steht,R 2 stands for cyano, thiocarbamoyl, fluorine, chlorine, bromine, or for alkyl with 1 to 4 carbon atoms optionally substituted by fluorine and / or chlorine, R 3 represents alkyl which has 1 to 6 carbon atoms and is optionally substituted by cyano, fluorine, chlorine, bromine, 0, -0 4 -alkoxy or C ] -C 4 -alkylthio,
R3 weiterhin für jeweils gegebenenfalls durch Fluor, Chlor und/oder Brom substituiertes Alkenyl oder Alkinyl mit jeweils 2 bis 6R 3 furthermore each represents alkenyl or alkynyl, each substituted by fluorine, chlorine and / or bromine, each having 2 to 6
Kohlenstoffatomen steht,Carbon atoms,
R3 weiterhin für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Brom oder C,-C4- Alkyl substituiertes Cycloalkyl oder Cycloalkyl¬ alkyl mit 3 bis 8 Kohlenstoffatomen im Cycloalkylteil und gege- benenfalls 1 bis 4 Kohlenstoffatomen im Alkylteil steht,R 3 furthermore represents cycloalkyl or cycloalkylalkyl with 3 to 8 carbon atoms in the cycloalkyl part and optionally 1 to 4 carbon atoms in the alkyl part, optionally substituted by cyano, fluorine, chlorine, bromine or C 1 -C 4 -alkyl,
R3 weiterhin für jeweils gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Nitro, Carboxy, Carbamoyl, Thiocarbamoyl, durch C C4- Alkyl, CrC4-Alkoxy, CrC4-Alkylthio, C,-C4-Alkylsulfιnyl oder C]-C4-Alkylsulfonyl (welche jeweils gegebenenfalls durch Fluor und/oder Chlor substituiert sind), durch Dimethylaminosulfonyl oderR 3 for each optionally by fluorine, chlorine, bromine, cyano, nitro, carboxy, carbamoyl, thiocarbamoyl, by CC 4 alkyl, C r C 4 alkoxy, C r C 4 alkylthio, C, -C 4 alkylsulfonyl or C ] -C 4 alkylsulfonyl (which are each optionally substituted by fluorine and / or chlorine), by dimethylaminosulfonyl or
Diethylaminosulfonyl, durch CrC4-Alkoxy-carbonyl (welches gege¬ benenfalls durch Fluor, Chlor, Brom, Cyano, Methoxy oder Ethoxy substituiert ist), durch Phenyl, Phenyloxy oder Phenylthio (welche jeweils gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Methyl, Methoxy, Trifluormethyl und/oder Trifluorm ethoxy substituiert sind) substituiertes Phenyl, Naphthyl, Benzyl, Phenylethyl, Thienyl, Pyrazolyl, Pyridinyl oder Chinolinyl steht,Diethylaminosulfonyl, by C r C 4 -alkoxy-carbonyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, methoxy or ethoxy), by phenyl, phenyloxy or phenylthio (which in each case optionally by fluorine, chlorine, bromine, cyano , Methyl, methoxy, trifluoromethyl and / or trifluoromethoxy are substituted) substituted phenyl, naphthyl, benzyl, phenylethyl, thienyl, pyrazolyl, pyridinyl or quinolinyl,
R4 für Wasserstoff, Fluor, Chlor, Brom oder für jeweils gegebenenfalls durch Fluor und/oder Chlor substituiertes Alkyl oder Alkoxy mit jeweils 1 bis 4 Kohlenstoffatomen steht, undR 4 represents hydrogen, fluorine, chlorine, bromine or alkyl or alkoxy, each optionally substituted by fluorine and / or chlorine, each having 1 to 4 carbon atoms, and
R5 für gegebenenfalls durch Fluor und/oder Chlor substituiertes Alkyl mit 1 bis 4 Kohlenstoffatomen steht.R 5 represents alkyl with 1 to 4 carbon atoms optionally substituted by fluorine and / or chlorine.
3. Aminouracile der allgemeinen Formel (I) gemäß Anspruch 1, dadurch gekennzeichnet, daß3. Aminouracile of the general formula (I) according to claim 1, characterized in that
R1 für Wasserstoff, Cyano, Fluor oder Chlor steht, R2 für Cyano, Thiocarbamoyl, Fluor, Chlor, Brom, Methyl, Difluor¬ methyl oder Trifluormethyl steht,R 1 represents hydrogen, cyano, fluorine or chlorine, R 2 represents cyano, thiocarbamoyl, fluorine, chlorine, bromine, methyl, difluoromethyl or trifluoromethyl,
R3 für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl steht,R 3 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,
R3 weiterhin für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Brom, Methyl, Ethyl, n- oder i-Propyl substituiertes Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl steht,R 3 furthermore represents cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl which is optionally substituted by cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl,
R3 weiterhin für jeweils gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Nitro, Carboxy, Carbamoyl, Thiocarbamoyl, Methyl, Ethyl, n- oder i-Propyl, Trifluormethyl, Methoxy, Ethoxy, n- oder i- Propoxy, Difluormethoxy, Trifluormethoxy, Methylthio, Ethylthio, n- oder i-Propylthio, Methylsulfmyl, Ethylsulfinyl, n- oder i-Propyl- sulfinyl, Methylsulfonyl, Ethylsulfonyl, n- oder i-Propylsulfonyl, Di- methylaminosulfonyl, Diethylaminosulfonyl, Methoxycarbonyl,R 3 for each optionally by fluorine, chlorine, bromine, cyano, nitro, carboxy, carbamoyl, thiocarbamoyl, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy , Methylthio, ethylthio, n- or i-propylthio, methylsulfmyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, dimethylaminosulfonyl, diethylaminosulfonyl, methoxycarbonyl,
Ethoxycarbonyl, n- oder i-Propoxycarbonyl substituiertes Phenyl, Naphthyl, Benzyl, Thienyl, Pyrazolyl oder Pyridinyl steht,Ethoxycarbonyl, n- or i-propoxycarbonyl substituted phenyl, naphthyl, benzyl, thienyl, pyrazolyl or pyridinyl,
R4 für Wasserstoff, Fluor, Chlor, Brom oder für jeweils gegebenenfalls durch Fluor und/oder Chlor substituiertes Methyl, Ethyl, n- oder i- Propyl steht, undR 4 represents hydrogen, fluorine, chlorine, bromine or methyl, ethyl, n- or i-propyl which is optionally substituted by fluorine and / or chlorine, and
R5 für gegebenenfalls durch Fluor und/oder Chlor substituiertes Methyl, Ethyl, n- oder i-Propyl steht.R 5 represents methyl, ethyl, n- or i-propyl optionally substituted by fluorine and / or chlorine.
4. Verfahren zur Herstellung von Aminouracilderivaten der allgemeinen4. Process for the preparation of aminouracil derivatives of the general
Formel (I)
Figure imgf000022_0001
in welcherFormula (I)
Figure imgf000022_0001
in which
R , 11, t R", τ K3ό, t R>4μ und R3 die in Anspruch 1 angegebenen Bedeutungen haben,R, 1 1 , t R " , τ K3 ό , t R> 4 μ and R 3 have the meanings given in claim 1,
dadurch gekennzeichnet, daß mancharacterized in that one
Uracilderivate der allgemeinen Formel (II)Uracil derivatives of the general formula (II)
Figure imgf000022_0002
Figure imgf000022_0002
in welcherin which
R ,ι , R »2~, R τ,3 , r R4 und R die oben angegebenen Bedeutungen haben,R, ι, R »2 ~, R τ, 3, r R4 and R have the meanings given above,
mit einem elektrophilen Aminierungsmittel, gegebenenfalls in Gegenwart eines Reaktionshilfsmittels und gegebenenfalls in Gegenwart eines Ver¬ dünnungsmittels umsetzt.with an electrophilic aminating agent, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent.
5. Herbizide Mittel, gekennzeichnet durch einen Gehalt an mindestens einem Aminouracilderivat der allgemeinen Formel (I) gemäß den Ansprüchen 1 bis 4. 5. Herbicidal agents, characterized in that they contain at least one aminouracil derivative of the general formula (I) according to Claims 1 to 4.
6. Verfahren zur Bekämpfung von unerwünschten Pflanzen, dadurch gekenn¬ zeichnet, daß man Aminouracilderivate der allgemeinen Formel (I) gemäß den Ansprüchen 1 bis 4 auf unerwünschte Pflanzen und/oder ihren Lebens¬ raum einwirken läßt.6. A method for controlling unwanted plants, characterized gekenn¬ characterized in that aminouracil derivatives of the general formula (I) according to claims 1 to 4 are allowed to act on undesirable plants and / or their habitat.
7. Verwendung von Aminouracilderivaten der allgemeinen Formel (I) gemäß der Ansprüche 1 bis 4 zur Bekämpfung von unerwünschten Pflanzen.7. Use of aminouracil derivatives of the general formula (I) according to Claims 1 to 4 for combating undesirable plants.
8. Verfahren zur Herstellung von herbiziden Mitteln, dadurch gekennzeichnet, daß man Aminouracilderivate der allgemeinen Formel (I) gemäß der An¬ sprüche 1 bis 4 mit Streckmitteln und/oder oberflächenaktiven Substanzen vermischt. 8. A process for the preparation of herbicidal compositions, characterized in that aminouracil derivatives of the general formula (I) according to Claims 1 to 4 are mixed with extenders and / or surface-active substances.
PCT/EP1996/001819 1995-05-15 1996-05-02 Aminouracil derivates WO1996036614A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0408382A2 (en) * 1989-07-14 1991-01-16 Nissan Chemical Industries, Limited Uracil derivatives and herbicides containing the same as active ingredient
WO1994004511A1 (en) * 1992-08-21 1994-03-03 Nissan Chemical Industries, Ltd. Pyrimidine derivative and weedkiller
EP0648749A2 (en) * 1993-08-18 1995-04-19 Bayer Ag N-cynanoaryl nitrogencontaining heterocycles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0408382A2 (en) * 1989-07-14 1991-01-16 Nissan Chemical Industries, Limited Uracil derivatives and herbicides containing the same as active ingredient
WO1994004511A1 (en) * 1992-08-21 1994-03-03 Nissan Chemical Industries, Ltd. Pyrimidine derivative and weedkiller
EP0648749A2 (en) * 1993-08-18 1995-04-19 Bayer Ag N-cynanoaryl nitrogencontaining heterocycles

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