WO2001068616A1 - Substituted 1-aryl-cyclopropylmethylamino-1,3,5-triazines - Google Patents

Substituted 1-aryl-cyclopropylmethylamino-1,3,5-triazines Download PDF

Info

Publication number
WO2001068616A1
WO2001068616A1 PCT/EP2001/002439 EP0102439W WO0168616A1 WO 2001068616 A1 WO2001068616 A1 WO 2001068616A1 EP 0102439 W EP0102439 W EP 0102439W WO 0168616 A1 WO0168616 A1 WO 0168616A1
Authority
WO
WIPO (PCT)
Prior art keywords
methyl
chlorine
fluorine
ethyl
substituted
Prior art date
Application number
PCT/EP2001/002439
Other languages
German (de)
French (fr)
Inventor
Stefan Herrmann
Hans-Jochem Riebel
Kristian Kather
Stefan Lehr
Mark-Wilhelm Drewes
Peter Dahmen
Dieter Feucht
Rolf Pontzen
Christoph Erdelen
Peter Lösel
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 AU2001248330A priority Critical patent/AU2001248330A1/en
Publication of WO2001068616A1 publication Critical patent/WO2001068616A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
    • C07D251/18—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom with nitrogen atoms directly attached to the two other ring carbon atoms, e.g. guanamines

Definitions

  • the invention relates to new substituted l-aryl-cyclopropylmethylamino-l, 3,5-triazines, ner processes for their preparation and their use as plant treatment agents, in particular as herbicides and as insecticides.
  • Ar represents in each case optionally substituted by hydroxyl, nitro, cyano, formyl, carboxyl, carbamoyl, thiocarbamoyl, halogen, C ⁇ -C 4 -alkyl, C haloalkyl, C ⁇ -C 4 -alkoxy, C 4 haloalkoxy, C ⁇ - C -alkylthio, C * -C 4 -haloalkyl-thio, -C-C 4 -alkylsulfmyl, C ⁇ -C 4 -haloalkylsulfmyl, C ⁇ -C -alkylsulfonyl, C ⁇ -C 4 -haloalkylsulfonyl, C ⁇ -C 4 -alkyl carbonyl, C 1 -C 4 alkoxycarbonyl, phenyl or phenoxy substituted phenyl, naphthyl, furyl.
  • R 1 for hydrogen, halogen, in each case optionally by hydroxy, cyano, halogen, C r C 4 alkoxy, C 1 -C 4 alkylthio, CC 4 alkyl sulfmyl or C 1 -C 4 - Alkylsulfonyl-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms, each optionally substituted by halogen-substituted alkenyl or alkynyl each having up to 6 carbon atoms, or optionally cycloalkyl substituted by cyano, halogen or C] -C 4 -alkyl 3 to 6 carbon atoms,
  • R 2 represents hydrogen or alkyl with 1 to 6 carbon atoms optionally substituted by cyano, halogen or CC 4 alkoxy, and
  • R 3 represents hydrogen, formyl, in each case optionally by cyano, halogen or
  • the compounds of the general formula (I) according to the invention contain at least one asymmetrically substituted carbon atom and can therefore be present in various enantiomeric (R- and S-configured) or diastereomeric forms.
  • the invention relates both to the various possible individual enantiomeric or stereoisomeric forms of the compounds of the general formula (I) and to the mixtures of these stereoisomeric compounds.
  • radicals R 1 , R 2 and R 3 are substituents with asymmetrically substituted carbon atoms, both the diastereomer mixtures which are possible in each case and the individual possible diastereomers are the subject of the invention.
  • Ar preferably represents in each case optionally by hydroxyl, nitro, cyano, formyl, carboxy, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, iodine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t -Butyl, difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl, chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, methylthio, ethylthio, n- or i-propylmethyl , Trifluoromethylthio, chlorodifluoromethylthio, methyl
  • R preferably represents hydrogen, fluorine, chlorine, bromine, in each case optionally by hydroxy, cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, methylsulfmyl, ethylsulfinyl, n- or i-pro - pylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n -, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n
  • R preferably represents hydrogen or methyl or ethyl which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy.
  • R 3 preferably represents hydrogen, formyl, in each case optionally by
  • Ar particularly preferably represents in each case optionally by cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, trifluoromethylthio,
  • R 1 particularly preferably represents in each case optionally by hydroxy, fluorine,
  • R, 2 particularly preferably represents hydrogen, methyl or ethyl.
  • R 3 particularly preferably represents hydrogen, formyl, methyl or ethyl, or acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl optionally substituted by fluorine, chlorine, methoxy or ethoxy , Methylaminocarbonyl, ethyl aminocarbonyl, n- or i-propylaminocarbonyl.
  • Ar very particularly preferably represents in each case optionally by cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, difluoromethylthio, trifluoromethylthio, methylsulfmyl, ethylsulfinyl, trifluoromethylsulfyl, methylsulfyl , Trifluoromethylsulfonyl, methoxycarbonyl or ethoxycarbonyl substituted phenyl or thienyl.
  • R 1 very particularly preferably represents methyl, ethyl, n-, i- or cyclo-propyl, each optionally substituted by fluorine, chlorine, bromine, methoxy, ethoxy, methylthio, ethylthio, methylsulfmyl, ethylsulfmyl, methylsulfonyl or ethylsulfonyl.
  • R very particularly preferably represents hydrogen.
  • R 3 very particularly preferably represents hydrogen, formyl, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, or phenylcarbonyl.
  • radical definitions listed above apply both to the end products of the formula (I) and correspondingly to the starting or intermediate products required in each case for the preparation. These radical definitions can be combined with one another, that is to say also between the specified preferred ranges.
  • Preferred compounds according to the invention are those of the formula (I) in which there is a combination of the meanings listed above as preferred. Particularly preferred according to the invention are those compounds of the formula (I) in which there is a combination of the meanings listed above as being particularly preferred.
  • the new substituted l-aryl-cyclopropylmethylamino-1,3,5-triazines of the general formula (I) have interesting biological properties. They are particularly characterized by strong herbicidal and insecticidal activity.
  • R has the meaning given above and R 'represents alkyl
  • the biguanides to be used as starting materials in the process according to the invention for the preparation of compounds of the general formula (I) are generally defined by the formula (II).
  • Ar, R and R preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the general formula (I) according to the invention preferably or as particularly preferred for Ar, R 2 and R 3 have been given.
  • Suitable acid adducts of compounds of formula (II) are their addition products with protonic acids, such as e.g. with hydrogen chloride (hydrogen chloride),
  • Hydrogen bromide (hydrogen bromide), sulfuric acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid.
  • the starting materials of the general formula (II) are not yet known from the literature; as new substances, they are also the subject of the present application.
  • reaction auxiliary such as hydrogen chloride
  • diluent such as toluene, n-decane or 1,2-dichlorobenzene
  • the biguanides of the general formula (II) can also be used directly for the preparation of the compounds of the general formula (I) by the process according to the invention without intermediate isolation.
  • the arylalkylamines of the general formula (IV) required as products are known and / or can be prepared by processes known per se (cf. DE-A-2526965, US-A-3781443, US-A-3840524, preparation examples).
  • Formula (III) provides a general definition of the alkoxycarbonyl 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 1 preferably or in particular has those meanings which have already been given above or in connection with the description of the compounds of the general formula (I) according to the invention as preferred or as particularly preferred for R 1 ;
  • R ' preferably represents alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl.
  • the starting materials of the general formula (III) are known synthetic chemicals.
  • diluents for carrying out the process according to the invention are in particular inert organic solvents. 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 ethylene glycol dimethyl or diethyl ether; Ketones, such as acetone, butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or
  • 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, hydrogen carbonates, 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,
  • 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.
  • 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 paths and squares with and without tree cover.
  • the active compounds according to the invention 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 as well as for selective purposes Weed control can be used 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 selective use
  • the active compounds according to the invention can also be used to control animal pests and fungal or bacterial plant diseases. They can be if used as intermediate or Vo ⁇ rodukte for the synthesis of other active ingredients.
  • 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 cultivated plants (including naturally occurring cultivated plants).
  • Cultivated 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 those by
  • Plant variety rights of protectable or non-protectable plant varieties Plant parts are to be understood to mean all above-ground and underground parts and organs of plants, such as sprout, leaf, flower and root, 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.
  • Storage room according to the usual treatment methods, e.g. by dipping, spraying, vaporizing, atomizing, scattering, spreading and, in the case of propagation material, in particular seeds, furthermore by single- or multi-layer coating.
  • the active ingredients can be converted into the usual formulations, such as
  • These formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, ie liquid solvents and / or solid carriers, optionally 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 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.
  • 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.
  • 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
  • suitable 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
  • 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.
  • Mineral and vegetable oils can also be used as additives.
  • 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 of active compound, 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 are therefore also possible possible with weed control agents which contain one or more known herbicides and a safener.
  • 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, azimsul matterson, benazolin (beflubutamide, ethyl), benfuresate, bensulfuron (-methyl), bentazone, benzfendizone, benzobicyclone, benzofenap, benzoylprop (-ethyl), bialaphos, bifenox, bispyribac (-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butafenacil (-allyl) , Butroxydim, Butylate, Cafenstrole, Caloxydim, Carbetamide,
  • Flumetsulam Flumiclorac (-pentyl), Flumioxazin, Flumipropyn, Flumetsulam, Fluometuron, Fluorochloridone, Fluoroglycofen (-ethyl), Flupoxam, Flupropacil, Flu ⁇ yr- sulfuron (-methyl, -sodium), Flurenol (-butyl), Flurypyrone (-butoxypropyl, -meptyl), fluorimidol, flurtamone, fluthiacet (-methyl), fluthiamide, fom-safen, foramsulfuron, glufosinate (-ammonium), glyphosate (-isopropylammonium), halosafen, haloxyfop (-ethoxyethyl, P -methyl), hexazinones, imazametha- benz (-methyl), imazamethapyr, imazamox, imazapic, imazapyr, im
  • 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, sprinkling.
  • 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.
  • 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 using the UV spectra from 200 nm to 400 nm in the maxima of the chromatographic signals.
  • a mixture of 19 g (0.13 mol) of cyclopropyl-phenyl-methylamine, 250 ml of toluene, 50 ml of 1,4-dioxane and 15.5 g of 30% hydrochloric acid is heated under reflux, the water contained therein on a water separator is separated. After adding 10.8 g (0.13 mol) of cyanoguanidine, the reaction mixture is then kept at 140 ° C. for two hours, then cooled to room temperature, stirred with acetone and the crystalline product is isolated by suction.
  • a mixture of 50 g (0.34 mol) of cyclopropylphenyl ketone and 150 g of formamide is heated to 150 ° C. and at this temperature 50 ml of formic acid are added dropwise over the course of 60 minutes.
  • the mixture is heated to 160 ° C. for a further 2 hours.
  • the mixture is diluted to about three times the volume with approximately equal volumes of water and toluene, shaken well, the organic phase is separated off, dried with sodium sulfate and filtered. The solvent is carefully distilled off from the filtrate under reduced pressure.
  • a mixture of 25 g (0.14 mol) of N- (cyclohexyl-phenyl-methyl) -formamide, 50 ml of conc. Hydrochloric acid and 50 ml of water are heated under reflux for 60 minutes. After cooling to room temperature, the mixture is filtered and the filtrate is adjusted to pH 10 by adding 20% sodium hydroxide solution. Then it is extracted with toluene, the organic phase is dried with sodium sulfate and filtered. The product is isolated from the filtrate by distillation under reduced pressure.
  • 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 selected 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 to 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 in
  • the degree of damage to the plants is rated in% damage compared to the development of the untreated control.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with horseradish leaf beetle larvae (Phaedon cochleariae) while the leaves are still moist.
  • the kill is determined in%. 100% means that all beetle larvae have been killed; 0% means that none of the beetle larvae have been killed.

Landscapes

  • 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)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to novel, substituted 1-aryl-cyclopropylamino-1,3,5-triazines of the general formula (I), wherein the groups R?1, R2, R3¿ and Ar are defined as in the description. The invention further relates to a method and to intermediates for producing the same and to their use as herbicides and insecticides.

Description

Substituierte l-Aryl-cvclopropylmethylamino-l,3 5-triazineSubstituted 1-aryl-cvclopropylmethylamino-1, 3 5-triazines
Die Erfindung betrifft neue substituierte l-Aryl-cyclopropylmethylamino-l,3,5-tri- azine, Nerfahren zu ihrer Herstellung und ihre Verwendung als Pflanzenbehandlungsmittel, insbesondere als Herbizide und als Insektizide.The invention relates to new substituted l-aryl-cyclopropylmethylamino-l, 3,5-triazines, ner processes for their preparation and their use as plant treatment agents, in particular as herbicides and as insecticides.
Eine Reihe von l-Aryl-alkylarnino-l,3,5-triazinen ist bereits aus der (Patent-)Litera- tur bekannt (vgl. US-A-3816419, US-A-3932167, WO-A-98/15536, WO-A- 98/42684, WO-A-99/18100). Diese Verbindungen haben jedoch bisher keine besondere Bedeutung erlangt.A number of l-aryl-alkylarnino-1,3,5-triazines are already known from the (patent) literature (cf. US-A-3816419, US-A-3932167, WO-A-98/15536 , WO-A-98/42684, WO-A-99/18100). However, these connections have so far not gained any particular importance.
Es wurden nun die neuen substituierten l-Aryl-cyclopropylamino-1.3.5-triazine der allgemeinen Formel (I)The new substituted l-aryl-cyclopropylamino-1,3.5-triazines of the general formula (I)
Figure imgf000002_0001
in welcher
Figure imgf000002_0001
in which
Ar für jeweils gegebenenfalls durch Hydroxy, Nitro, Cyano, Formyl, Carboxy, Carbamoyl, Thiocarbamoyl, Halogen, Cι-C4-Alkyl, Cι-C -Halogenalkyl, Cι-C4-Alkoxy, Cι-C4-Halogenalkoxy, Cι-C -Alkylthio, C*-C4-Halogenalkyl- thio, Cι-C4-Alkylsulfmyl, Cι-C4-Halogenalkylsulfmyl, Cι-C -Alkylsulfonyl, Cι-C4-Halogenalkylsulfonyl, Cι-C4-Alkyl-carbonyl, Cι-C4-Alkoxy-carbonyl, Phenyl oder Phenoxy substituiertes Phenyl, Naphthyl, Furyl. Thienyl, Oxa- zolyl, Thiazolyl, Pyridinyl oder Pyrimidinyl steht,Ar represents in each case optionally substituted by hydroxyl, nitro, cyano, formyl, carboxyl, carbamoyl, thiocarbamoyl, halogen, Cι-C 4 -alkyl, C haloalkyl, Cι-C 4 -alkoxy, C 4 haloalkoxy, Cι- C -alkylthio, C * -C 4 -haloalkyl-thio, -C-C 4 -alkylsulfmyl, Cι-C 4 -haloalkylsulfmyl, Cι-C -alkylsulfonyl, Cι-C 4 -haloalkylsulfonyl, Cι-C 4 -alkyl carbonyl, C 1 -C 4 alkoxycarbonyl, phenyl or phenoxy substituted phenyl, naphthyl, furyl. Thienyl, oxazolyl, thiazolyl, pyridinyl or pyrimidinyl,
R1 für Wasserstoff, Halogen, jeweils gegebenenfalls durch Hydroxy, Cyano, Halogen, CrC4-Alkoxy, Cι-C4-Alkylthio, C C4-Alkylsulfmyl oder Cι-C4- Alkylsulfonyl substituiertes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl oder Alkylsulfonyl mit jeweils 1 bis 6 Kohlenstoffatomen, jeweils gegebenenfalls durch Halogen substituiertes Alkenyl oder Alkinyl mit jeweils bis zu 6 Kohlenstoffatomen, oder gegebenenfalls durch Cyano, Halogen oder C]-C4- Alkyl substituiertes Cycloalkyl mit 3 bis 6 Kohlenstoffatomen steht,R 1 for hydrogen, halogen, in each case optionally by hydroxy, cyano, halogen, C r C 4 alkoxy, C 1 -C 4 alkylthio, CC 4 alkyl sulfmyl or C 1 -C 4 - Alkylsulfonyl-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms, each optionally substituted by halogen-substituted alkenyl or alkynyl each having up to 6 carbon atoms, or optionally cycloalkyl substituted by cyano, halogen or C] -C 4 -alkyl 3 to 6 carbon atoms,
R ,2 für Wasserstoff oder jeweils gegebenenfalls durch Cyano, Halogen oder C C4-Alkoxy substituiertes Alkyl mit 1 bis 6 Kohlenstoffatomen steht, undR 2 represents hydrogen or alkyl with 1 to 6 carbon atoms optionally substituted by cyano, halogen or CC 4 alkoxy, and
R3 für Wasserstoff, Formyl, jeweils gegebenenfalls durch Cyano, Halogen oderR 3 represents hydrogen, formyl, in each case optionally by cyano, halogen or
Cj-C4-Alkoxy substituiertes C--C -Alkyl, C C -Alkyl-carbonyl, Cι-C - Alkoxy-carbonyl oder Cι-C4-Alkylamino-carbonyl, oder Phenylcarbonyl steht,C 1 -C 4 -alkoxy-substituted C 1 -C 4 -alkyl, CC 4 -alkyl carbonyl, C 1 -C 4 -alkoxy carbonyl or C 1 -C 4 -alkylamino-carbonyl, or phenylcarbonyl,
gefunden.found.
Die erfindungsgemäßen Verbindungen der allgemeinen Formel (I) enthalten mindestens ein asymmetrisch substituiertes Kohlenstoffatom und können deshalb in verschiedenen enantiomeren (R- und S-konfigurierten) bzw. diastereomeren Formen vorliegen. Die Erfindung betrifft sowohl die verschiedenen möglichen einzelnen enantiomeren bzw. stereoisomeren Formen der Verbindungen der allgemeinen Formel (I) wie auch die Gemische dieser stereoisomeren Verbindungen.The compounds of the general formula (I) according to the invention contain at least one asymmetrically substituted carbon atom and can therefore be present in various enantiomeric (R- and S-configured) or diastereomeric forms. The invention relates both to the various possible individual enantiomeric or stereoisomeric forms of the compounds of the general formula (I) and to the mixtures of these stereoisomeric compounds.
Sofern die Reste R1, R2 und R3 für Substituenten mit asymmetrisch substituierten Kohlenstoffatomen stehen, sind sowohl die jeweils möglichen Diastereomerenge- mische als auch die einzelnen möglichen Diastereomeren Gegenstand der Erfindung.If the radicals R 1 , R 2 and R 3 are substituents with asymmetrically substituted carbon atoms, both the diastereomer mixtures which are possible in each case and the individual possible diastereomers are the subject of the invention.
Bevorzugte Substituenten bzw. Bereiche der in den oben und nachstehend aufgeführten Formeln vorhandenen Reste werden im Folgenden beschrieben. Ar steht bevorzugt für jeweils gegebenenfalls durch Hydroxy, Nitro, Cyano, Formyl, Carboxy, Carbamoyl, Thiocarbamoyl, Fluor, Chlor, Brom, lod, Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Difluormethyl, Tri- fluormethyl, Dichlormethyl, Trichlormethyl, Chlordifluormethyl, Fluordi- chlormethyl, Methoxy, Ethoxy, n- oder i-Propoxy, Difluormethoxy, Trifluor- methoxy, Chlordifluormethoxy, Methylthio, Ethylthio, n- oder i-Propylthio, Difluormethylthio, Trifluormethylthio, Chlordifluormethylthio, Methyl- sulfinyl, Ethylsulfinyl, n- oder i-Propylsulfmyl, Trifluormethylsulfinyl, Chlordifluormethylsulfmyl, Methylsulfonyl, Ethylsulfonyl, n- oder i-Propyl- sulfonyl, Trifluormethylsulfonyl, Chlor-difluormethylsulfonyl, Acetyl, Pro- pionyl, n- oder i-Butyroyl, Methoxycarbonyl, Ethoxycarbonyl, n- oder i-Prop- oxycarbonyl, Phenyl oder Phenoxy substituiertes Phenyl, Naphthyl, Furyl, Thienyl, Oxazoyl, Thiazolyl, Pyridinyl oder Pyrimidinyl.Preferred substituents or ranges of the radicals present in the formulas listed above and below are described below. Ar preferably represents in each case optionally by hydroxyl, nitro, cyano, formyl, carboxy, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, iodine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t -Butyl, difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl, chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, methylthio, ethylthio, n- or i-propylmethyl , Trifluoromethylthio, chlorodifluoromethylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfmyl, trifluoromethylsulfinyl, chlordifluoromethylsulfmyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, trifluoromethylsulfonyl, acylsulfonyl, nodyl, n-propylsulfonyl, n-propylsulfonyl, n-propylsulfonyl, n-propylsulfonyl, acylsulfonyl, n-propylsulfonyl, n-propylsulfonyl, acylsulfonyl, n-propylsulfonyl, acylsulfonyl, n-propylsulfonyl, acylsulfonyl, n-propylsulfonyl, acylsulfonyl, n-propylsulfonyl, n-propylsulfonyl, acyl or methyl-diformonyl, trifluoromethylsulfonyl, acylsulfonyl, n-propylsulfonyl, acyl or methyl, i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-prop-oxycarbonyl, phenyl or phenoxy substituted phenyl, naphthyl, furyl, thienyl, oxazoyl, thiazolyl, pyridinyl or pyrimidinyl.
R steht bevorzugt für Wasserstoff, Fluor, Chlor, Brom, jeweils gegebenenfalls durch Hydroxy, Cyano, Fluor, Chlor, Brom, Methoxy, Ethoxy, n- oder i- Propoxy, Methylthio, Ethylthio, Methylsulfmyl, Ethylsulfinyl, n- oder i-Pro- pylsulfinyl, Methylsulfonyl, Ethylsulfonyl, n- oder i-Propylsulfonyl 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, n-, i-, s- oder t-Butylthio, Methylsulfmyl, Ethylsulfinyl, n- oder i-Propylsulfmyl, Methylsulfonyl, Ethylsulfonyl, n- oder i-Propylsulf- onyl, jeweils gegebenenfalls durch Fluor, Chlor oder Brom substituiertes Ethenyl, Propenyl, Butenyl, Ethinyl, Propinyl oder Butinyl, oder jeweils ge- gebenenfalls durch Cyano, Fluor, Chlor, Brom, Methyl oder Ethyl substituiertes Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl.R preferably represents hydrogen, fluorine, chlorine, bromine, in each case optionally by hydroxy, cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, methylsulfmyl, ethylsulfinyl, n- or i-pro - pylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n -, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfmyl, ethylsulfinyl, n- or i-propylsulfmyl, methylsulfonyl, ethylsulfonyl , n- or i-Propylsulfonyl, each optionally substituted by fluorine, chlorine or bromine, ethenyl, propenyl, butenyl, ethynyl, propynyl or butynyl, or in each case optionally substituted by cyano, fluorine, chlorine, bromine, methyl or ethyl cyclopropyl , Cyclobutyl, cyclopentyl or cyclohexyl.
R steht bevorzugt für Wasserstoff oder für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl oder Ethyl. R3 steht bevorzugt für Wasserstoff, für Formyl, für jeweils gegebenenfalls durchR preferably represents hydrogen or methyl or ethyl which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy. R 3 preferably represents hydrogen, formyl, in each case optionally by
Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl, Ethyl,Cyano, fluorine, chlorine, methoxy or ethoxy substituted methyl, ethyl,
Acetyl, Propionyl, n- oder i-Butyroyl, Methoxycarbonyl, Ethoxycarbonyl, n- oder i-Propoxycarbonyl, Methylaminocarbonyl, Ethylammocarbonyl, n- oder i-Propylaminocarbonyl, oder für Phenylcarbonyl.Acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, ethylammocarbonyl, n- or i-propylaminocarbonyl, or for phenylcarbonyl.
Ar steht besonders bevorzugt für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Brom, Methyl, Ethyl, n- oder i-Propyl, Trifluormethyl, Methoxy, Ethoxy, n- oder i-Propoxy, Difluormethoxy, Trifluormethoxy, Methylthio, Ethylthio, n- oder i-Propylthio, Difiuormethylthio, Trifluormethylthio,Ar particularly preferably represents in each case optionally by cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio,
Methylsulfmyl, Ethylsulfinyl, Trifluormethylsulfinyl, Methylsulfonyl, Ethylsulfonyl, Trifluormethylsulfonyl, Methoxycarbonyl, Ethoxycarbonyl, Phenyl oder Phenoxy substituiertes Phenyl, Thienyl, Thiazolyl oder Pyridinyl.Methylsulfmyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl, methoxycarbonyl, ethoxycarbonyl, phenyl or phenoxy substituted phenyl, thienyl, thiazolyl or pyridinyl.
R1 steht besonders bevorzugt für jeweils gegebenenfalls durch Hydroxy, Fluor,R 1 particularly preferably represents in each case optionally by hydroxy, fluorine,
Chlor, Brom, Methoxy, Ethoxy, Methylthio, Ethylthio, Methylsulfmyl, Ethylsulfinyl, Methylsulfonyl oder Ethylsulfonyl substituiertes Methyl, Ethyl, n- oder i-Propyl, Methoxy, Ethoxy, n- oder i-Propoxy, Methylthio, Ethylthio, n- oder i-Propylthio, Methylsulfmyl, Ethylsulfinyl, Methylsulfonyl oder Ethyl- sulfonyl, jeweils gegebenenfalls durch Fluor, Chlor oder Brom substituiertesChlorine, bromine, methoxy, ethoxy, methylthio, ethylthio, methylsulfmyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i -Propylthio, methylsulfmyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, each optionally substituted by fluorine, chlorine or bromine
Ethenyl, Propenyl, Butenyl, Ethinyl, Propinyl oder Butinyl, oder gegebenenfalls durch Fluor, Chlor oder Methyl substituiertes Cyclopropyl.Ethenyl, propenyl, butenyl, ethynyl, propynyl or butynyl, or cyclopropyl optionally substituted by fluorine, chlorine or methyl.
R ,2 steht besonders bevorzugt für Wasserstoff, Methyl oder Ethyl.R, 2 particularly preferably represents hydrogen, methyl or ethyl.
R3 steht besonders bevorzugt für Wasserstoff, für Formyl, für Methyl oder Ethyl, oder für jeweils gegebenenfalls durch Fluor, Chlor, Methoxy oder Ethoxy substituiertes Acetyl, Propionyl, n- oder i-Butyroyl, Methoxycarbonyl, Ethoxycarbonyl, n- oder i-Propoxycarbonyl, Methylaminocarbonyl, Ethyl- aminocarbonyl, n- oder i-Propylaminocarbonyl. Ar steht ganz besonders bevorzugt für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Brom, Methyl, Ethyl, Trifluormethyl, Methoxy, Ethoxy, Di- fluormethoxy, Trifluormethoxy, Methylthio, Ethylthio, Difluormethylthio, Trifluormethylthio, Methylsulfmyl, Ethylsulfinyl, Trifluormethylsulfinyl, Methylsulfonyl, Ethylsulfonyl, Trifluormethylsulfonyl, Methoxycarbonyl oder Ethoxycarbonyl substituiertes Phenyl oder Thienyl.R 3 particularly preferably represents hydrogen, formyl, methyl or ethyl, or acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl optionally substituted by fluorine, chlorine, methoxy or ethoxy , Methylaminocarbonyl, ethyl aminocarbonyl, n- or i-propylaminocarbonyl. Ar very particularly preferably represents in each case optionally by cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, difluoromethylthio, trifluoromethylthio, methylsulfmyl, ethylsulfinyl, trifluoromethylsulfyl, methylsulfyl , Trifluoromethylsulfonyl, methoxycarbonyl or ethoxycarbonyl substituted phenyl or thienyl.
R1 steht ganz besonders bevorzugt für jeweils gegebenenfalls durch Fluor, Chlor, Brom, Methoxy, Ethoxy, Methylthio, Ethylthio, Methylsulfmyl, Ethyl- sulfmyl, Methylsulfonyl oder Ethylsulfonyl substituiertes Methyl, Ethyl, n-, i- oder cyclo-Propyl.R 1 very particularly preferably represents methyl, ethyl, n-, i- or cyclo-propyl, each optionally substituted by fluorine, chlorine, bromine, methoxy, ethoxy, methylthio, ethylthio, methylsulfmyl, ethylsulfmyl, methylsulfonyl or ethylsulfonyl.
R steht ganz besonders bevorzugt für Wasserstoff.R very particularly preferably represents hydrogen.
R3 steht ganz besonders bevorzugt für Wasserstoff, für Formyl, für jeweils gegebenenfalls durch Fluor, Chlor, Methoxy oder Ethoxy substituiertes Acetyl, Propionyl, n- oder i-Butyroyl, Methoxycarbonyl, Ethoxycarbonyl, n- oder i- Propoxycarbonyl, oder für Phenylcarbonyl.R 3 very particularly preferably represents hydrogen, formyl, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, or phenylcarbonyl.
Die oben aufgeführten allgemeinen oder in Vorzugsbereichen aufgeführten Restedefinitionen gelten sowohl für die Endprodukte der Formel (I) als auch entsprechend für die jeweils zur Herstellung benötigten Ausgangs- oder Zwischenprodukte. Diese Restedefinitionen können untereinander, also auch zwischen 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 or intermediate products required in each case for the preparation. These radical definitions can be combined with one another, that is to say also between the specified preferred ranges.
Erfindungsgemäß bevorzugt sind diejenigen Verbindungen der Formel (I), bei welchen eine Kombination der vorstehend als bevorzugt aufgeführten Bedeutungen vorliegt. Erfmdungsgemäß besonders bevorzugt sind diejenigen Verbindungen der Formel (I), bei welchen eine Kombination der vorstehend als besonders bevorzugt aufgeführten Bedeutungen vorliegt.Preferred compounds according to the invention are those of the formula (I) in which there is a combination of the meanings listed above as preferred. Particularly preferred according to the invention are those compounds of the formula (I) in which there is a combination of the meanings listed above as being particularly preferred.
Erfindungsgemäß ganz besonders bevorzugt sind diejenigen Verbindungen der Formel (I), bei welchen eine Kombination der vorstehend als ganz besonders bevorzugt aufgerührten Bedeutungen vorliegt.Those compounds of the formula (I) which have a combination of the meanings mentioned above as being very particularly preferred are very particularly preferred according to the invention.
Die neuen substituierten l-Aryl-cyclopropylmethylamino-l,3,5-triazine der allge- meinen Formel (I) weisen interessante biologische Eigenschaften auf. Sie zeichnen sich insbesondere durch starke herbizide und durch insektizide Wirksamkeit aus.The new substituted l-aryl-cyclopropylmethylamino-1,3,5-triazines of the general formula (I) have interesting biological properties. They are particularly characterized by strong herbicidal and insecticidal activity.
Man erhält die substituierten l-Aryl-cyclopropylmethylamino-l,3,5-triazine der allgemeinen Formel (I), wenn man Biguanide der allgemeinen Formel (II)The substituted l-aryl-cyclopropylmethylamino-1,3,5-triazines of the general formula (I) are obtained if biguanides of the general formula (II)
Figure imgf000007_0001
in welcher
Figure imgf000007_0001
in which
Ar, R und R die oben angegebene Bedeutung haben,Ar, R and R have the meaning given above,
- und/oder Säureaddukte von Verbindungen der allgemeinen Formel (II)and / or acid adducts of compounds of the general formula (II)
mit Alkoxycarbonylverbindungen der allgemeinen Formel (III) R'-CO-OR' (III) in welcherwith alkoxycarbonyl compounds of the general formula (III) R'-CO-OR '(III) in which
R die oben angegebene Bedeutung hat und R' für Alkyl steht,R has the meaning given above and R 'represents alkyl,
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,
und gegebenenfalls an den so erhaltenen Verbindungen der allgemeinen Formel (I) im Rahmen der Substituentendefinition weitere Umwandlungen nach üblichen Methoden durchführt.and optionally on the compounds of the general formula (I) thus obtained, as part of the definition of the substituent, carries out further conversions by customary methods.
Verwendet man beispielsweise l-(Thien-2-yl-cyclopropyl-methyl)-biguanid und 2-For example, if 1- (thien-2-yl-cyclopropyl-methyl) -biguanide and 2-
Fluor-propansäure-methylester als Ausgangsstoffe, so kann der Reaktionsablauf beim erfmdungsgemäßen Verfahren durch das folgende Formelschema skizziert werden:Fluoropropanoic acid methyl ester as starting materials, the course of the reaction in the process according to the invention can be outlined using the following formula:
Figure imgf000008_0001
Figure imgf000008_0001
Die beim erfindungsgemäßen Verfahren zur Herstellung von Verbindungen der allgemeinen Formel (I) als Ausgangsstoffe zu verwendenden Biguanide sind durch die Formel (II) allgemein definiert. In der allgemeinen Formel (II) haben Ar, R und R vorzugsweise bzw. insbesondere diejenigen Bedeutungen, die bereits oben im Zu- sammenhang mit der Beschreibung der erfindungsgemäßen Verbindungen der allgemeinen Formel (I) vorzugsweise bzw. als insbesondere bevorzugt für Ar, R2 und R3 angegeben worden sind.The biguanides to be used as starting materials in the process according to the invention for the preparation of compounds of the general formula (I) are generally defined by the formula (II). In the general formula (II), Ar, R and R preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the general formula (I) according to the invention preferably or as particularly preferred for Ar, R 2 and R 3 have been given.
Geeignete Säureaddukte von Verbindungen der Formel (II) sind deren Additions- produkte mit Protonensäuren, wie z.B. mit Chlorwasserstoff (Hydrogenchlorid),Suitable acid adducts of compounds of formula (II) are their addition products with protonic acids, such as e.g. with hydrogen chloride (hydrogen chloride),
Bromwasserstoff (Hydrogenbromid), Schwefelsäure, Methansulfonsäure, Benzol- sulfonsäure und p-Toluolsulfonsäure. Die Ausgangsstoffe der allgemeinen Formel (II) sind noch nicht aus der Literatur bekannt; sie sind als neue Stoffe auch Gegenstand der vorliegenden Anmeldung.Hydrogen bromide (hydrogen bromide), sulfuric acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid. The starting materials of the general formula (II) are not yet known from the literature; as new substances, they are also the subject of the present application.
Man erhält die neuen Biguanide der allgemeinen Formel (II), wenn man Aryl-cyclo- propyl-methylamine der allgemeinen Formel (IN)The new biguanides of the general formula (II) are obtained if aryl-cyclopropylmethylamines of the general formula (IN)
Figure imgf000009_0001
in welcher
Figure imgf000009_0001
in which
Ar die oben angegebene Bedeutung hat,Ar has the meaning given above,
- und/oder Säureaddukte von Verbindungen der allgemeinen Formel (IV), wie z.B. die Hydrochloride -and / or acid adducts of compounds of the general formula (IV), such as e.g. the hydrochloride -
mit Cyanoguanidin („Dicyandiamid") der Formel (V)with cyanoguanidine ("dicyandiamide") of the formula (V)
Figure imgf000009_0002
gegebenenfalls in Gegenwart eines Reaktionshilfsmittels, wie z.B. Hydrogenchlorid, und gegebenenfalls in Gegenwart eines Verdünnungsmittels, wie z.B. Toluol, n- Decan oder 1,2-Dichlor-benzol, bei Temperaturen zwischen 100°C und 200°C umsetzt (vgl. die Herstellungsbeispiele).
Figure imgf000009_0002
if appropriate in the presence of a reaction auxiliary, such as hydrogen chloride, and if appropriate in the presence of a diluent, such as toluene, n-decane or 1,2-dichlorobenzene, at temperatures between 100 ° C. and 200 ° C. (cf. the preparation examples) ,
Die Biguanide der allgemeinen Formel (II) können nach ihrer Herstellung auch ohne Zwischenisolierung direkt zur Herstellung der Verbindungen der allgemeinen Formel (I) nach dem erfindungsgemäßen Verfahren eingesetzt werden. Die als Voφrodukte benötigten Arylalkylamine der allgemeinen Formel (IV) sind bekannt und/oder können nach an sich bekannten Verfahren hergestellt werden (vgl. DE-A-2526965, US-A-3781443, US-A-3840524, Herstellungsbeispiele).After their preparation, the biguanides of the general formula (II) can also be used directly for the preparation of the compounds of the general formula (I) by the process according to the invention without intermediate isolation. The arylalkylamines of the general formula (IV) required as products are known and / or can be prepared by processes known per se (cf. DE-A-2526965, US-A-3781443, US-A-3840524, preparation examples).
Die beim erfindungsgemäßen Verfahren zur Herstellung von Verbindungen der allgemeinen Formel (I) weiter als Ausgangsstoffe zu verwendenden Alkoxycarbonyl- verbindungen sind durch die Formel (III) allgemein definiert. In der allgemeinen Formel (III) hat R1 vorzugsweise bzw. insbesondere diejenigen Bedeutungen, die bereits oben im Zusammenhang mit der Beschreibung der erfindungsgemäßen Ver- bindungen der allgemeinen Formel (I) vorzugsweise bzw. als insbesondere bevorzugt für R1 angegeben worden sind; R' steht vorzugsweise für Alkyl mit 1 bis 4 Kohlenstoffatomen, insbesondere für Methyl oder Ethyl.Formula (III) provides a general definition of the alkoxycarbonyl 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 (III), R 1 preferably or in particular has those meanings which have already been given above or in connection with the description of the compounds of the general formula (I) according to the invention as preferred or as particularly preferred for R 1 ; R 'preferably represents alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl.
Die Ausgangsstoffe der allgemeinen Formel (III) sind bekannte Synthesechemika- lien.The starting materials of the general formula (III) are known synthetic chemicals.
Das erfindungsgemäße Verfahren zur Herstellung der Verbindungen der allgemeinen Formel (I) wird vorzugsweise unter Verwendung eines Verdünnungsmittels durchgeführt. Als Verdünnungsmittel zur Durchführung des erfindungsgemäßen Verfahrens kommen neben Wasser vor allem inerte organische Lösungsmittel in Betracht. Hierzu gehören insbesondere aliphatische, alicyclische oder aromatische, gegebenenfalls halogenierte Kohlenwasserstoffe, wie beispielsweise Benzin, Benzol, Toluol, Xylol, Chlorbenzol, Dichlorbenzol, Petrolether, Hexan, Cyclohexan, Dichlormethan, Chloroform, Tetrachlorkohlenstoff; Ether, wie Diethylether, Diisopropylether, Dioxan, Tetrahydrofüran oder Ethylenglykoldimethyl- oder -diethylether; Ketone, wie Ace- ton, Butanon oder Methyl-isobutyl-keton; Nitrile, wie Acetonitril, Propionitril oder Butyronitril; Amide, wie N,N-Dimethylformamid, N,N-Dimethylacetamid, N- Methyl-formanilid, N-Methyl-pyrrolidon oder Hexamethylphosphorsäuretriamid; 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.The process according to the invention for the preparation of the compounds of the general formula (I) is preferably carried out using a diluent. In addition to water, diluents for carrying out the process according to the invention are in particular inert organic solvents. 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 ethylene 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-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric 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 mono- methyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, their mixtures with water or pure water.
Als Reaktionshilfsmittel für das erfindungsgemäße Verfahren kommen im allgemei- nen 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-, Kaliumoder Calcium-amid, Natrium-, Kalium- oder Calcium-carbonat, Natrium-, Kalium- oder Calcium-hydrogencarbonat, Lithium-, Natrium-, Kalium- oder Calcium-hydrid,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, hydrogen carbonates, 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-, 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 Trimethyl- amin, Triethylamin, Tripropylamin, Tributylamin, Ethyl-diisopropylamin, N,N-Di- methyl-cyclohexylamin, Dicyclohexylamin, Ethyl-dicyclohexylamin, N,N-Dimethyl- anilin, N,N-Dimethyl-benzylamin, Pyridin, 2-Methyl-, 3-Methyl-, 4-Methyl-, 2,4-Di- methyl-, 2,6-Dimethyl-, 3,4-Dimethyl- und 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 1,8-Diazabicyclo- [5.4.0]-undec-7-en (DBU).Lithium, sodium, potassium or calcium hydroxide, sodium or potassium methoxide, ethanolate, n or i propanolate, n, i, i or t butanolate; also basic organic nitrogen compounds, such as 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-methylpyridine, 4-dimethylamino-pyridine, N-methylpiperidine, 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).
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.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 erfindungsgemäßen Verfahren unter erhöhtem oder vermindertem Druck - im allgemeinen zwischen 0,1 bar und 10 bar - durchzu- führen. 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).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. 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.The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers.
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.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: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum,Dicotyledon weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, 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, Rorippex, Rotal Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.
Dikotyle Kulturen der Gattungen: Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia. Monokotyle Unkräuter der Gattungen: 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, Sciφus, Setaria, Sorghum.Dicotyledon cultures of the genera: Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia. Monocotyledonous weeds of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Fistula, Eriocha, Antherocho, Eriocha, Antherocho , Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Sciφus, 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 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 erfindungsgemäßen Wirkstoffe eignen sich in Abhängigkeit von der Konzentration zur Totalunkrautbekämpfüng, z.B. auf Industrie- und Gleisanlagen und auf Wegen und Plätzen mit und ohne Baumbewuchs. Ebenso können die erfindungsgemäßen Wirkstoffe zur Unkrautbekämpfung in Dauerkulturen, 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 einjährigen Kulturen eingesetzt werden.Depending 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 paths and squares with and without tree cover. The active compounds according to the invention 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 as well as for selective purposes Weed control can be used in annual crops.
Die erfindungsgemäßen Verbindungen der Formel (I) zeigen starke herbizide Wirksamkeit und ein breites Wirkungsspektrum bei Anwendung auf dem Boden und auf oberirdische Pflanzenteile. Sie eignen sich in gewissem Umfang auch zur selektivenThe 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 selective use
Bekämpfung von monokotylen und dikotylen Unkräutern in monokotylen und di- kotylen Kulturen, sowohl im Vorauflauf- als auch im Nachauflauf-Verfahren.Control of monocot and dicot weeds in monocot and dicotyledon crops, both pre- and post-emergence.
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 Voφrodukte 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. They can be if used as intermediate or Voφrodukte for the synthesis of other active ingredients.
Erfindungsgemäß können alle Pflanzen und Pflanzenteile behandelt werden. Unter Pflanzen werden hierbei alle Pflanzen und Pflanzenpopulationen verstanden, wie erwünschte und unerwünschte Wildpflanzen oder Kultuφflanzen (einschließlich natürlich vorkommender Kultuφflanzen). Kultuφflanzen 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 durchAccording 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 cultivated plants (including naturally occurring cultivated plants). Cultivated 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 those by
Sortenschutzrechte schützbaren oder nicht schützbaren Pflanzensorten. 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, Fruchtköφer, Früchte und Samen sowie Wurzeln, Knollen und Rhizome aufgeführt werden. Zu den Pflanzenteilen gehört auch Erntegut sowie vegetatives und generatives Vermehrungsmaterial, beispielsweise Stecklinge, Knollen, Rhizome, Ableger und Samen.Plant variety rights of protectable or non-protectable plant varieties. Plant parts are to be understood to mean all above-ground and underground parts and organs of plants, such as sprout, leaf, flower and root, 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 Wirk- Stoffen erfolgt direkt oder durch Einwirkung auf deren Umgebung, Lebensraum oderThe treatment of the plants and plant parts according to the invention with the active substances takes place directly or by acting on their environment, habitat or
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.Storage room according to the usual treatment methods, e.g. by dipping, spraying, vaporizing, atomizing, scattering, spreading and, in the case of propagation material, in particular seeds, furthermore by single- or multi-layer coating.
Die Wirkstoffe können in die üblichen Formulierungen übergeführt werden, wieThe active ingredients can be converted into the usual formulations, such as
Lösungen, Emulsionen, Spritzpulver, Suspensionen, Pulver, Stäubemittel, Pasten, lösliche Pulver, Granulate, Suspensions-Emulsions-Konzentrate, Wirkstoff-imprägnierte Natur- und synthetische Stoffe sowie Feinstverkapselungen in polymeren Stoffen. Diese Formulierungen werden in bekannter Weise hergestellt, z. B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugen- den Mitteln.Solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances as well as very fine encapsulations in polymeric substances. These formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, ie liquid solvents and / or solid carriers, optionally 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, wieIf 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
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.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, Talkum, Kreide, Quarz, Attapulgit, Mont- morillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate, als feste Trägerstoffe für Granulate kommen in Frage: z.B. gebrochene und f aktionierte 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 schaum- erzeugende Mittel kommen in Frage: z.B. nichtionogene und anionische Emulgato- ren, wie Polyoxyethylen-Fettsäure-Ester, Polyoxyethylen-Fettalkohol-Ether, z.B. Alkylarylpolyglykolether, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweiß- hydrolysate; als Dispergiermittel kommen in Frage: z.B. Lignin-Sulfitablaugen und Methylcellulose. 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 Addi- tive können mineralische und vegetabile Öle sein.The following are suitable as solid carriers: for example 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 Question: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable 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; Possible dispersing agents are, for example, lignin sulfite waste 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. Mineral and vegetable oils can also be used as additives.
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 Gewichtsprozent 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 Formulierungen auch in Mischung mit bekannten Herbiziden und/oder mit Stoffen, welche die Kultuφflanzen- 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 are therefore also possible possible with weed control agents which contain one or more known herbicides and a safener.
Für die Mischungen kommen bekannte Herbizide infrage, beispielsweise Acetochlor, Acifluorfen (-sodium), Aclonifen, Alachlor, Alloxydim (-sodium), Ametryne, Amicarbazone, Amidochlor, Amidosulfuron, Anilofos, Asulam, Atrazine, Azafenidin, Azimsulfüron, Beflubutamid, Benazolin (-ethyl), Benfuresate, Bensulf- uron (-methyl), Bentazon, Benzfendizone, Benzobicyclon, Benzofenap, Benzoylprop (-ethyl), Bialaphos, Bifenox, Bispyribac (-sodium), Bromobutide, Bromofenoxim, 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, Clopyrasulfüron (-methyl), Clor- ansulam (-methyl), Cumyluron, Cyanazine, Cybutryne, Cycloate, Cyclosulfamuron, Cycloxydim, Cyhalofop (-butyl), 2,4-D, 2,4-DB, Desmedipham, Diallate, Dicamba, Dichloφrop (-P), Diclofop (-methyl), Diclosulam, Diethatyl (-ethyl), Difenzoquat, Diflufenican, Diflufenzopyr, Dimefuron, Dimepiperate, Dimethachlor, Dimetha- metryn, Dimethenamid, Dimexyflam, Dinitramine, Diphenamid, Diquat, Dithiopyr, Diuron, Dymron, Epropodan, EPTC, Esprocarb, Ethalflurahn, Ethametsulfuron (-methyl), Ethofumesate, Ethoxyfen, Ethoxysulfuron, Etobenzanid, Fenoxaprop (-P- ethyl), Fentrazamide, Flamprop (-isopropyl, -isopropyl-L, -methyl), Flazasulfüron, Florasulam, Fluazifop (-P-butyl), Fluazolate, Flucarbazone (-sodium), Flufenacet,Known herbicides are suitable for the mixtures, for example acetochlor, acifluorfen (-sodium), aclonifen, alachlor, alloxydim (-sodium), ametryne, amicarbazone, amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafenidin, azimsulfüron, benazolin (beflubutamide, ethyl), benfuresate, bensulfuron (-methyl), bentazone, benzfendizone, benzobicyclone, benzofenap, benzoylprop (-ethyl), bialaphos, bifenox, bispyribac (-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butafenacil (-allyl) , Butroxydim, Butylate, Cafenstrole, Caloxydim, Carbetamide, Carfentrazone (-ethyl), Chlomethoxyfen, Chloramben, Chloridazon, Chlorimuron (-ethyl), Chlornitrofen, Chlorsulfuron, Chlortoluron, Cinidone (-ethyl), Cinmethylin, Clefoximimuron , Clodinafop (-propargyl), Clomazone, Clomeprop, Clopyralid, Clopyrasulfüron (-methyl), Clor-ansulam (-methyl), Cumyluron, Cyanazine, Cybutryne, Cycloate, Cyclosulfamuron, Cycloxydim, Cyhalofop (-butyl), 2,4-D, 2 , 4-DB, Desmedipham, Diallate, Dicamba, Dichloφrop (-P), Diclofop (-methyl), Diclosulam, Diethatyl (-ethyl), Difenzoquat, Diflufenican, Diflufenzopyr, Dimefuron, Dimepiperate, Dimethachlor, Dimethamamidyn, Dimxyamide , Dinitramine, Diphenamid, Diquat, Dithiopyr, Diuron, Dymron, Epropodan, EPTC, Esprocarb, Ethalflurahn, Ethametsulfuron (-methyl), Ethofumesate, Ethoxyfen, Ethoxysulfuron, Etobenzanid, Fenoxaprop (-P-ethyl), Fentrazamide, Flentrazamide, Flentrazamide -isopropyl-L, -methyl), flazasulfüron, florasulam, fluazifop (-P-butyl), fluazolates, flucarbazone (-sodium), flufenacet,
Flumetsulam, Flumiclorac (-pentyl), Flumioxazin, Flumipropyn, Flumetsulam, Fluo- meturon, Fluorochloridone, Fluoroglycofen (-ethyl), Flupoxam, Flupropacil, Fluφyr- sulfuron (-methyl, -sodium), Flurenol (-butyl), Fluridone, Fluroxypyr (-butoxypro- pyl, -meptyl), Fluφrimidol, Flurtamone, Fluthiacet (-methyl), Fluthiamide, Fome- safen, Foramsulfuron, Glufosinate (-ammonium), Glyphosate (-isopropylammo- nium), Halosafen, Haloxyfop (-ethoxyethyl, -P -methyl), Hexazinone, Imazametha- benz (-methyl), Imazamethapyr, Imazamox, Imazapic, Imazapyr, Imazaquin, Imaz- ethapyr, Imazosulfuron, Iodosulfuron (-methyl, -sodium), Ioxynil, Isopropalin, Iso- proturon, Isouron, Isoxaben, Isoxachlortole, Isoxaflutole, Isoxapyrifop, Lactofen, Lenacil, Linuron, MCPA, Mecoprop, Mefenacet, Mesotrione, Metamitron, Metaza- chlor, Methabenzthiazuron, Metobenzuron, Metobromuron, (alpha-) Metolachlor, Metosulam, Metoxuron, Metribuzin, Metsulfuron (-methyl), Molinate, Monolinuron, Naproanilide, Napropamide, Neburon, Nicosulfuron, Norflurazon, Orbencarb, Oryzalin, Oxadiargyl, Oxadiazon, Oxasulfuron, Oxaziclomefone, Oxyfluorfen, Para- quat, Pelargonsäure, Pendimethalin, Pendralin, Pentoxazone, Phenmedipham, Pico- linafen, Piperophos, Pretilachlor, Primisulfuron (-methyl), Profluazol, Prometryn, Propachlor, Propanil, Propaquizafop, Propisochlor, Procarbazone (-sodium), Propyz- amide, Prosulfocarb, Prosulfuron, Pyraflufen (-ethyl), Pyrazogyl, Pyrazolate, Pyrazo- sulfuron (-ethyl), Pyrazoxyfen, Pyribenzoxim, Pyributicarb, Pyridate, Pyridatol, Pyri- ftalid, Pyriminobac (-methyl), Pyrithiobac (-sodium), Quinchlorac, Quinmerac, Quin- oclamine, Quizalofop (-P-ethyl, -P-tefuryl), Rimsulfuron, Sethoxydim, Simazine, Simetryn, Sulcotrione, Sulfentrazone, Sulfometuron (-methyl), Sulfosate, Sulfosulf- uron, Tebutam, Tebuthiuron, Tepraloxydim, Terbuthylazine, Terbutryn, Thenylchlor, Thiafluamide, Thiazopyr, Thidiazimin, Thifensulfuron (-methyl), Thiobencarb, Tio- carbazil, Tralkoxydim, Triallate, Triasulfüron, Tribenuron (-methyl), Triclopyr, Tri- diphane, Trifluralin, Trifloxysulfuron, Triflusulfuron (-methyl), Tritosulfuron.Flumetsulam, Flumiclorac (-pentyl), Flumioxazin, Flumipropyn, Flumetsulam, Fluometuron, Fluorochloridone, Fluoroglycofen (-ethyl), Flupoxam, Flupropacil, Fluφyr- sulfuron (-methyl, -sodium), Flurenol (-butyl), Flurypyrone (-butoxypropyl, -meptyl), fluorimidol, flurtamone, fluthiacet (-methyl), fluthiamide, fom-safen, foramsulfuron, glufosinate (-ammonium), glyphosate (-isopropylammonium), halosafen, haloxyfop (-ethoxyethyl, P -methyl), hexazinones, imazametha- benz (-methyl), imazamethapyr, imazamox, imazapic, imazapyr, imazaquin, imaz-ethapyr, imazosulfuron, iodosulfuron (-methyl, -sodium), ioxynil, isopropalin, iso-proturon, isouron Isoxaben, Isoxachlortole, Isoxaflutole, Isoxapyrifop, Lactofen, Lenacil, Linuron, MCPA, Mecoprop, Mefenacet, Mesotrione, Metamitron, Metazachlor, Methabenzthiazuron, Metobenzuron, Metobromuron, (alpha-) Metolachlor, Metobromuron, Metobromuron, Metolamonuronamuronamuronamuronuronamuronuramuronamuronamuronuronamuronuramuronamuronuramuronamuronamuronuramuronuramuronuramuronamuronuroxamonuramuronuroxamonoxuramuronamuronamuroxuramuronamuroxuramuronamuroxuramuroxamonoxuramuroxuramurin ), Molinate, Monolinuron, Naproanilide, Napropamide, Neburon, Nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pendralin, pentoxazone, phenmedipham, pico-linafen, piperophos, pretiluronol, promet Propachlor, propanil, propaquizafop, propisochlor, procarbazone (-sodium), propyz-amide, prosulfocarb, prosulfuron, pyraflufen (-ethyl), pyrazogyl, pyrazolate, pyrazo-sulfurone (-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarbolide, pyributicarbolide, pyributicarbolide, Pyrifalid, Pyriminobac (-methyl), Pyrithiobac (-sodium), Quinchlorac, Quinmerac, Quinoclamine, Quizalofop (-P-ethyl, -P-tefuryl), Rimsulfuron, Sethoxydim, Simazine, Simetryn, Sulcotrione, Sulfentrazone, Sulfometuron (-methyl), Sulfosate, Sulfosulfuron, Tebutam, Tebuthiuron, Tepraloxydim, Terbuthylazine, Terbutryn, Thenylchlor, Thiafluamide, Thiazopyr, Thidiazimin, Thifensulfuron-, carboximiloxyl, carbazyl, carbaziloxymiloximiloximiloximiloximiloximiloximiloximiloximiloximiloximiloximiloximiloximiloxi Triallates, triasulfuron, tribenuron (-methyl), triclopyr, tri-diphane, trifluralin, trifloxysulfuron, triflusulfuron (-methyl), tritosulfuron.
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, Streuen.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, 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 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.
Die Herstellung und die Verwendung der erfindungsgemäßen Wirkstoffe geht aus den nachfolgenden Beispielen hervor. Herstellungsbeispiele:The preparation and use of the active compounds according to the invention can be seen from the examples below. Preparation Examples:
Beispiel 1example 1
Figure imgf000019_0001
10,0 g (37,5 mMol) l-(Phenyl-cyclopropyl-methyl)-biguanid-Hydrochlorid werden in 80 ml Methanol vorgelegt und mit 5,0 g (47 mMol) 2-Fluor-propansäure-methyl- ester (racemisch) versetzt. Zu dieser Mischung werden unter Rühren 7,2 ml einer 30%igen Lösung von Natriummethanolat in Methanol tropfenweise gegeben. Die Reaktionsmischung wird dann 15 Stunden bei Raumtemperatur (ca. 20°C) gerührt, anschließend mit etwa gleichen Volumenmengen Wasser und Methylenchlorid auf etwa das dreifache Volumen verdünnt und gut durchgeschüttelt. Die organische Phase wird abgetrennt und die wässrige Phase noch zweimal mit Methylenchlorid nachextrahiert. Die vereinigten organischen Phasen werden mit Natriumsulfat getrocknet und filtriert. Vom Filtrat wird das Lösungsmittel unter vermindertem Druck sorgfältig abdestilliert.
Figure imgf000019_0001
10.0 g (37.5 mmol) of 1- (phenyl-cyclopropyl-methyl) -biguanide hydrochloride are placed in 80 ml of methanol and mixed with 5.0 g (47 mmol) of methyl 2-fluoropropanoate (racemic ) offset. 7.2 ml of a 30% solution of sodium methoxide in methanol are added dropwise to this mixture with stirring. The reaction mixture is then stirred for 15 hours at room temperature (approx. 20 ° C.), then diluted to approximately three times the volume with approximately equal volumes of water and methylene chloride and shaken well. The organic phase is separated off and the aqueous phase is extracted twice more with methylene chloride. The combined organic phases are dried with sodium sulfate and filtered. The solvent is carefully distilled off from the filtrate under reduced pressure.
Man erhält 5,8 g (54 % der Theorie) N2-(Cyclopropyl-phenyl-methyl)-6-(l-fluor- ethyl)-l,3,5-triazin-2,4-diamin (Racemat) als amoφhen Rückstand.5.8 g (54% of theory) of N 2 - (cyclopropyl-phenyl-methyl) -6- (l-fluoro-ethyl) -l, 3,5-triazine-2,4-diamine (racemate) are obtained as amorous residue.
LogP (bei pH=2,3): 1,69. LogP (at pH = 2.3): 1.69.
Beispiel 2Example 2
Figure imgf000020_0001
Figure imgf000020_0001
Eine Mischung aus 5,8 g (20 mMol) N2-(Cyclopropyl -phenyl -methyl)-6-(l-fluor- ethyl)-l,3,5-triazin-2,4-diamin (racemisch), 2,8 g (23,5 mMol) N,N-Dimethyl-form- amid-dimethylacetal und 50 ml 1,4-Dioxan wird 15 Stunden bei Raumtemperatur (ca. 20°C) gerührt, anschließend mit 150 ml Wasser und 5 ml konz. Salzsäure verdünnt und weitere zwei Stunden gerührt. Das kristallin angefallene Produkt wird dann durch Absaugen isoliert.A mixture of 5.8 g (20 mmol) of N 2 - (cyclopropylphenylmethyl) -6- (l-fluoroethyl) -l, 3,5-triazine-2,4-diamine (racemic), 2 , 8 g (23.5 mmol) of N, N-dimethylformamide-dimethylacetal and 50 ml of 1,4-dioxane is stirred for 15 hours at room temperature (approx. 20 ° C.), then with 150 ml of water and 5 ml conc. Diluted hydrochloric acid and stirred for a further two hours. The crystalline product is then isolated by suction.
Man erhält 2,6 g (41 % der Theorie) N-[4-(Cyclopropyl-phenyl-methylamino)-6-(l- fluor-ethyl)-l,3,5-triazin-2-yl]-formamid (Racemat) vom Schmelzpunkt 148°C.2.6 g (41% of theory) of N- [4- (cyclopropylphenylmethylamino) -6- (l-fluoro-ethyl) -l, 3,5-triazin-2-yl] formamide ( Racemate) with a melting point of 148 ° C.
LogP (bei pH=2,3): 2,53.LogP (at pH = 2.3): 2.53.
Analog zu den Beispielen 1 und 2 sowie entsprechend der allgemeinen Beschreibung des erfindungsgemäßen Herstellungsverfahrens können beispielsweise auch die in der nachstehenden Tabelle 1 aufgeführten Verbindungen der allgemeinen Formel (I) hergestellt werden. Soweit nicht anders angegeben ist, handelt es sich hierbei um racemische Verbindungen bzw. Diastereomerengemische.Analogously to Examples 1 and 2 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 general formula (I) listed in Table 1 below. Unless otherwise stated, these are racemic compounds or diastereomer mixtures.
Figure imgf000020_0002
Tabelle 1: Beispiele für die Verbindungen der Formel (I)
Figure imgf000020_0002
Table 1: Examples of the compounds of the formula (I)
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000023_0001
Die Bestimmung der in Tabelle 1 angegebenen logP -Werte erfolgte gemäß EEC- Directive 79/831 Annex V.A8 durch HPLC (High Performance Liquid Chromato- graphy) an einer Phasenumkehrsäule (C 18). Temperatur: 43°C. (a) Eluenten für die Bestimmung im sauren Bereich: 0,1 %> wässrige Phosphorsäure, Acetonitril; linearer Gradient von 10 % Acetonitril bis 90 % Acetonitril - entsprechende Messergebnisse sind in Tabelle 1 mit a) markiert.The logP values given in Table 1 were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a phase inversion column (C 18). Temperature: 43 ° C. (a) Eluents for determination in the acidic range: 0.1%> aqueous phosphoric acid, 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 D) 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 D ).
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 Inteφolation 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. The lambda max values were determined using the UV spectra from 200 nm to 400 nm in the maxima of the chromatographic signals.
Ausgangsstoffe der Formel (II):Starting materials of formula (II):
Beispiel (H-l)Example (H-l)
Figure imgf000025_0001
Figure imgf000025_0001
Eine Mischung aus 19 g (0,13 Mol) Cyclopropyl-phenyl-methylamin, 250 ml Toluol, 50 ml 1,4-Dioxan und 15,5 g 30%>iger Salzsäure wird unter Rückfluß erhitzt, wobei das darin enthaltene Wasser am Wasserabscheider abgetrennt wird. Nach Zugabe von 10,8 g (0,13 Mol) Cyanoguanidin wird die Reaktionsmischung dann zwei Stunden bei 140°C gehalten, anschließend auf Raumtemperatur abgekühlt, mit Aceton verrührt und das kristalline Produkt durch Absaugen isoliert.A mixture of 19 g (0.13 mol) of cyclopropyl-phenyl-methylamine, 250 ml of toluene, 50 ml of 1,4-dioxane and 15.5 g of 30% hydrochloric acid is heated under reflux, the water contained therein on a water separator is separated. After adding 10.8 g (0.13 mol) of cyanoguanidine, the reaction mixture is then kept at 140 ° C. for two hours, then cooled to room temperature, stirred with acetone and the crystalline product is isolated by suction.
Man erhält 21,5 g (62 % der Theorie) l-(Phenyl-cyclopropyl-methyl)-biguanid-Hy- drochlorid vom Schmelzpunkt 260°C.21.5 g (62% of theory) of 1- (phenyl-cyclopropyl-methyl) -biguanide hydrochloride with a melting point of 260 ° C. are obtained.
Analog zu Beispiel (II- 1) können beispielsweise auch die in der nachstehendenAnalogous to example (II-1), for example, those in the following can also
Tabelle 2 aufgeführten Verbindungen der allgemeinen Formel (II) hergestellt werden.Compounds of general formula (II) listed in Table 2 can be prepared.
Figure imgf000025_0002
Tabelle 2: Beispiele für die Verbindungen der Formel (II)
Figure imgf000025_0002
Table 2: Examples of the compounds of the formula (II)
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000026_0001
Figure imgf000027_0001
Ausgangsstoffe der Formel (IN):Starting materials of the formula (IN):
Beispiel (IN-1)Example (IN-1)
Figure imgf000028_0001
Figure imgf000028_0001
Stufe 1step 1
Figure imgf000028_0002
Figure imgf000028_0002
Eine Mischung aus 50 g (0,34 Mol) Cyclopropyl-phenyl-keton und 150 g Formamid wird auf 150°C erhitzt und bei dieser Temperatur werden 50 ml Ameisensäure inner- halb von 60 Minuten tropfenweise dazu gegeben. Die Mischung wird weitere 2 Stunden auf 160°C erhitzt. Nach Abkühlen auf Raumtemperatur wird mit etwa gleichen Nolumenmengen Wasser und Toluol auf etwa das dreifache Volumen verdünnt, gut durchgeschüttelt, die organische Phase abgetrennt, mit Νatriumsulfat getrocknet und filtriert. Vom Filtrat wird das Lösungsmittel unter vermindertem Druck sorgfältig ab- destilliert.A mixture of 50 g (0.34 mol) of cyclopropylphenyl ketone and 150 g of formamide is heated to 150 ° C. and at this temperature 50 ml of formic acid are added dropwise over the course of 60 minutes. The mixture is heated to 160 ° C. for a further 2 hours. After cooling to room temperature, the mixture is diluted to about three times the volume with approximately equal volumes of water and toluene, shaken well, the organic phase is separated off, dried with sodium sulfate and filtered. The solvent is carefully distilled off from the filtrate under reduced pressure.
Man erhält 45 g (76 % der Theorie) Ν-(Cyclohexyl-phenyl-methyl)-formamid als öligen Rückstand.45 g (76% of theory) of Ν- (cyclohexyl-phenyl-methyl) -formamide are obtained as an oily residue.
Dieses Rohprodukt kann ohne weitere Reinigung weiter umgesetzt werden. Stufe 2This raw product can be used without further purification. Level 2
Figure imgf000029_0001
Figure imgf000029_0001
Eine Mischung aus 25 g (0,14 Mol) N-(Cyclohexyl-phenyl-methyl)-formamid, 50 ml konz. Salzsäure und 50 ml Wasser wird 60 Minuten unter Rückfluss erhitzt. Nach Abkühlen auf Raumtemperatur wird filtriert und das Filtrat durch Zugabe von 20%iger Natronlauge auf den pH- Wert 10 eingestellt. Dann wird mit Toluol extrahiert, die organische Phase mit Natriumsulfat getrocknet und filtriert. Aus dem Filtrat wird das Produkt durch Destillation unter vermindertem Druck isoliert.A mixture of 25 g (0.14 mol) of N- (cyclohexyl-phenyl-methyl) -formamide, 50 ml of conc. Hydrochloric acid and 50 ml of water are heated under reflux for 60 minutes. After cooling to room temperature, the mixture is filtered and the filtrate is adjusted to pH 10 by adding 20% sodium hydroxide solution. Then it is extracted with toluene, the organic phase is dried with sodium sulfate and filtered. The product is isolated from the filtrate by distillation under reduced pressure.
Man erhält 8,0 g (98 % der Theorie) Cyclopropyl-phenyl-methylamin vom Siedepunkt 58°C (bei 1 mbar). 8.0 g (98% of theory) of cyclopropyl-phenyl-methylamine with a boiling point of 58 ° C. (at 1 mbar) are obtained.
Anwendungsbeispiele: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 selected 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 1, 2, 3, 4, 5, 6 und 7 bei zum Teil guter Verträglichkeit gegenüber Kultuφflanzen, wie z.B. Weizen, starke Wirkung gegen Unkräuter.
Figure imgf000031_0001
In this test, the compounds according to preparation example 1, 2, 3, 4, 5, 6 and 7, for example, with strong tolerance to cultivated plants, such as, for example, wheat, show a strong action against weeds.
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000033_0001
Tabelle A4: Pre-emergence-Test GewächshausTable A4: Pre-emergence test greenhouse
Figure imgf000034_0001
Figure imgf000034_0001
Tabelle A4: Pre-emergence-Test GewächshausTable A4: Pre-emergence test greenhouse
Figure imgf000035_0001
Figure imgf000035_0001
Beispiel BExample 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 bis 15 cm haben so, dass die jeweils gewünschten Wirkstoffmengen pro Flächeneinheit ausgebracht werden. Die Konzentration der Spritzbrühe wird so gewählt, dass inTest plants with a height of 5 to 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 in
1000 1 Wasser/ha die jeweils gewünschten Wirkstoffmengen ausgebracht werden.1000 1 water / ha the desired amounts of active ingredient 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 1, 2, 3, 4, 5, 6 und 7 starke Wirkung gegen Unkräuter.
Figure imgf000037_0001
In this test, for example, the compounds according to Preparation Example 1, 2, 3, 4, 5, 6 and 7 show a strong action against weeds.
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000038_0002
Figure imgf000038_0001
Figure imgf000038_0002
Figure imgf000039_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000040_0002
Figure imgf000040_0001
Figure imgf000040_0002
Tabelle B2: Post-emergence-Test GewächshausTable B2: Post emergence test greenhouse
Figure imgf000041_0001
Figure imgf000041_0001
Beispiel CExample C
Phaedon-Larven-TestPhaedon larvae test
Lösungsmittel: 31 Gewichtsteile AcetonSolvent: 31 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 und der angegebe- nen Menge Emulgator 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 and the stated amount of emulsifier, and the concentrate is diluted with water to the desired level
Konzentration.Concentration.
Kohlblätter (Brassica oleracea) werden durch Tauchen in die Wirkstoffzubereitung der gewünschten Konzentration behandelt und mit Meerrettichblattkäfer-Larven (Phaedon cochleariae) besetzt, solange die Blätter noch feucht sind.Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with horseradish leaf beetle larvae (Phaedon cochleariae) while the leaves are still moist.
Nach der gewünschten Zeit wird die Abtötung in % bestimmt. Dabei bedeutet 100 %, dass alle Käfer-Larven abgetötet wurden; 0 % bedeutet, dass keine Käfer-Larven abgetötet wurden.After the desired time, the kill is determined in%. 100% means that all beetle larvae have been killed; 0% means that none of the beetle larvae have been killed.
In diesem Test zeigen z.B. die Verbindungen gemäß Herstellungsbeispiel 3 und 7 bei einer Wirkstoffkonzentration von 1000 ppm jeweils einen Abtötungsgrad von 100 % nach 7 Tagen. In this test, for example, the compounds according to Preparation Examples 3 and 7, with an active ingredient concentration of 1000 ppm, each show a degree of kill of 100% after 7 days.
Tabelle CTable C.
Pflanzenschädigende InsektenPlant-damaging insects
Phaedon-Larven-TestPhaedon larvae test
Figure imgf000043_0001
Figure imgf000043_0001

Claims

Patentansprüche claims
1. Verbindungen der allgemeinen Formel (I)1. Compounds of the general formula (I)
Figure imgf000044_0001
in welcher
Figure imgf000044_0001
in which
Ar für jeweils gegebenenfalls durch Hydroxy, Nitro, Cyano, Formyl, Carboxy, Carbamoyl, Thiocarbamoyl, Halogen, Cι-C -Alkyl, C*-C4- Halogenalkyl, Cι-C4-Alkoxy, Cι-C4-Halogenalkoxy, Cι-C4-Alkylthio, C C4-Halogenalkylthio, CrC4-Alkylsulfinyl, Cι-C4-Halogenalkyl- sulfinyl, Cι-C - Alkylsulfonyl, C*-C4-Halogenalkylsulfonyl, Cι-C4- Alkyl-carbonyl, Cι-C4-Alkoxy-carbonyl, Phenyl oder Phenoxy substituiertes Phenyl, Naphthyl, Furyl, Thienyl, Oxazolyl, Thiazolyl, Pyridinyl oder Pyrimidinyl steht,Ar represents in each case optionally substituted by hydroxyl, nitro, cyano, formyl, carboxyl, carbamoyl, thiocarbamoyl, halogen, Cι-C alkyl, C * -C 4 - haloalkyl, Cι-C 4 -alkoxy, C 4 haloalkoxy, Cι -C 4 -alkylthio, CC 4 -haloalkylthio, C r C 4 -alkylsulfinyl, -C-C 4 -haloalkyl-sulfinyl, Cι-C - alkylsulfonyl, C * -C 4 -haloalkylsulfonyl, Cι-C 4 - alkyl-carbonyl, C 1 -C 4 -alkoxy-carbonyl, phenyl or phenoxy-substituted phenyl, naphthyl, furyl, thienyl, oxazolyl, thiazolyl, pyridinyl or pyrimidinyl,
R! für Wasserstoff, Halogen, jeweils gegebenenfalls durch Hydroxy, Cyano, Halogen, C C4- Alkoxy, C C4- Alkylthio, Cι-C -Alkylsulfinyl oder C]-C4- Alkylsulfonyl substituiertes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl oder Alkylsulfonyl mit jeweils 1 bis 6 Kohlenstoff- atomen, jeweils gegebenenfalls durch Halogen substituiertes Alkenyl oder Alkinyl mit jeweils bis zu 6 Kohlenstoffatomen, oder gegebenenfalls durch Cyano, Halogen oder d-C4- Alkyl substituiertes Cycloal- kyl mit 3 bis 6 Kohlenstoffatomen steht,R ! for hydrogen, halogen, each optionally substituted by hydroxy, cyano, halogen, CC 4 -alkoxy, CC 4 -alkylthio, C 1 -C 4 -alkylsulfinyl or C] -C 4 -alkylsulfonyl-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl, each with 1 up to 6 carbon atoms, each optionally substituted by halogen-substituted alkenyl or alkynyl each having up to 6 carbon atoms, or optionally cycloalkyl having 3 to 6 carbon atoms substituted by cyano, halogen or dC 4 -alkyl,
R2 für Wasserstoff oder jeweils gegebenenfalls durch Cyano, Halogen oder C]-C4- Alkoxy substituiertes Alkyl mit 1 bis 6 Kohlenstoffatomen steht und R für Wasserstoff, Formyl, jeweils gegebenenfalls durch Cyano, Halogen oder Cι-C -Alkoxy substituiertes C1-C -Alkyl, Cι-C4-Alkyl- carbonyl, Cι-C4-Alkoxy-carbonyl oder Cι-C4-Alkylamino-carbonyl, oder Phenylcarbonyl steht.R 2 stands for hydrogen or alkyl with 1 to 6 carbon atoms which is optionally substituted by cyano, halogen or C] -C 4 - alkoxy and R is hydrogen, formyl, in each case optionally cyano-, halogen- or Cι-C -alkoxy-substituted C 1 -C -alkyl, C 4 alkyl carbonyl, Cι-C 4 -alkoxy-carbonyl or Cι-C 4 alkylamino -carbonyl, or phenylcarbonyl.
2. Verbindungen gemäß Anspruch 1, dadurch gekennzeichnet, dass2. Compounds according to claim 1, characterized in that
Ar für jeweils gegebenenfalls durch Hydroxy, Nitro, Cyano, Formyl, Carboxy, Carbamoyl, Thiocarbamoyl, Fluor, Chlor, Brom, lod,Ar for each optionally by hydroxy, nitro, cyano, formyl, carboxy, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, iodine,
Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Difluormethyl, Trifluormethyl, Dichlormethyl, Trichlormethyl, Chlordifluormethyl, Fluordichlormethyl, Methoxy, Ethoxy, n- oder i-Propoxy, Difluor- methoxy, Trifluormethoxy, Chlordifluormethoxy, Methylthio, Ethyl- thio, n- oder i-Propylthio, Difluormethylthio, Trifluormethylthio,Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl, chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy , Trifluoromethoxy, chlorodifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio,
Chlordifluormethylthio, Methylsulfmyl, Ethylsulfinyl, n- oder i-Pro- pylsulfinyl, Trifluormethylsulfmyl, Chlordifluormethylsulfinyl, Methylsulfonyl, Ethylsulfonyl, n- oder i-Propylsulfonyl, Trifluor- methylsulfonyl, Chlor-difluormethylsulfonyl, Acetyl, Propionyl, n- oder i-Butyroyl, Methoxycarbonyl, Ethoxycarbonyl, n- oder i-Propoxycarbonyl, Phenyl oder Phenoxy substituiertes Phenyl, Naphthyl, Furyl, Thienyl, Oxazoyl, Thiazolyl, Pyridinyl oder Pyrimidinyl steht,Chlorodifluoromethylthio, methylsulfmyl, ethylsulfinyl, n- or i-propylsulfinyl, trifluoromethylsulfmyl, chlordifluoromethylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, trifluoromethylsulfonyl, chloronifylyloxy, nyl-difluoromethyl, n-chloro-difluoromethyl, acyl-difluoromyl-n-oxyl-methyl-n-iodonyl-methyl-iodonyl-methyl-n-iodonyl-methyl-n-iodonyl, , Ethoxycarbonyl, n- or i-propoxycarbonyl, phenyl or phenoxy substituted phenyl, naphthyl, furyl, thienyl, oxazoyl, thiazolyl, pyridinyl or pyrimidinyl,
R1 für Wasserstoff, Fluor, Chlor, Brom, jeweils gegebenenfalls durch Hydroxy, Cyano, Fluor, Chlor, Brom, Methoxy, Ethoxy, n- oder i-R 1 represents hydrogen, fluorine, chlorine, bromine, in each case optionally by hydroxy, cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i-
Propoxy, Methylthio, Ethylthio, Methylsulfmyl, Ethylsulfinyl, n- oder i-Propylsulfinyl, Methylsulfonyl, Ethylsulfonyl, n- oder i-Propylsulf- onyl 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, n-, i-, s- oder t-Butylthio,Propoxy, methylthio, ethylthio, methylsulfmyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t- butylthio,
Methylsulfmyl, Ethylsulfinyl, n- oder i-Propylsulfinyl, Methylsulf- onyl, Ethylsulfonyl, n- oder i-Propylsulfonyl, jeweils gegebenenfalls durch Fluor, Chlor oder Brom substituiertes Ethenyl, Propenyl, Bute- nyl, Ethinyl, Propinyl oder Butinyl, oder jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Brom, Methyl oder Ethyl substituiertes Cyclo- propyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl steht,Methylsulfmyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfinyl onyl, ethylsulfonyl, n- or i-propylsulfonyl, each optionally substituted by fluorine, chlorine or bromine, ethenyl, propenyl, butenyl, ethynyl, propynyl or butynyl, or in each case optionally substituted by cyano, fluorine, chlorine, bromine, methyl or ethyl Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,
R2 für Wasserstoff oder für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl oder Ethyl steht undR 2 represents hydrogen or methyl or ethyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy and
R für Wasserstoff, für Formyl, für jeweils gegebenenfalls durch Cyano,R for hydrogen, for formyl, for each optionally by cyano,
Fluor, Chlor, Methoxy oder Ethoxy substituiertes Methyl, Ethyl, Acetyl, Propionyl, n- oder i-Butyroyl, Methoxycarbonyl, Ethoxycarbonyl, n- oder i-Propoxycarbonyl, Methylaminocarbonyl, Ethyl- aminocarbonyl, n- oder i-Propylaminocarbonyl, oder für Phenylcarb- onyl steht.Fluorine, chlorine, methoxy or ethoxy substituted methyl, ethyl, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl, or for phenylcarb - onyl stands.
3. Verbindungen gemäß Anspruch 1, dadurch gekennzeichnet, dass3. Compounds according to claim 1, characterized in that
Ar für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Brom, Methyl,Ar for each optionally by cyano, fluorine, chlorine, bromine, methyl,
Ethyl, n- oder i-Propyl, Trifluormethyl, Methoxy, Ethoxy, n- oder i- Propoxy, Difluormethoxy, Trifluormethoxy, Methylthio, Ethylthio, n- oder i-Propylthio, Difluormethylthio, Trifluormethylthio, Methylsulfmyl, Ethylsulfinyl, Trifluormethylsulfinyl, Methylsulfonyl, Ethyl- sulfonyl, Trifluormethylsulfonyl, Methoxycarbonyl, Ethoxycarbonyl,Ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, methylsulfmyl, ethylsulfinyl, trifluoromethylsulfyl, trifluoromethyl sulfonyl, trifluoromethylsulfonyl, methoxycarbonyl, ethoxycarbonyl,
Phenyl oder Phenoxy substituiertes Phenyl, Thienyl, Thiazolyl oder Pyridinyl steht,Phenyl or phenoxy substituted phenyl, thienyl, thiazolyl or pyridinyl,
R1 für jeweils gegebenenfalls durch Hydroxy, Fluor, Chlor, Brom, Methoxy, Ethoxy, Methylthio, Ethylthio, Methylsulfmyl, Ethylsulfinyl, Methylsulfonyl oder Ethylsulfonyl substituiertes Methyl, Ethyl, n- oder i-Propyl, Methoxy, Ethoxy, n- oder i-Propoxy, Methylthio, Ethylthio, n- oder i-Propylthio, Methylsulfmyl, Ethylsulfinyl, Methylsulfonyl oder Ethylsulfonyl, jeweils gegebenenfalls durch Fluor, Chlor oder Brom substituiertes Ethenyl, Propenyl, Butenyl, Ethinyl, Propinyl oder Butmyl, oder gegebenenfalls durch Fluor, Chlor oder Methyl substituiertes Cyclopropyl steht,R 1 for each methyl optionally substituted by hydroxy, fluorine, chlorine, bromine, methoxy, ethoxy, methylthio, ethylthio, methylsulfmyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, Ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfmyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, each optionally substituted by fluorine, chlorine or bromine, Propenyl, butenyl, ethynyl, propynyl or butmyl, or cyclopropyl optionally substituted by fluorine, chlorine or methyl,
R , 2 für Wasserstoff, Methyl oder Ethyl steht undR, 2 represents hydrogen, methyl or ethyl and
R , 3 für Wasserstoff, für Formyl, für Methyl oder Ethyl, oder für jeweils gegebenenfalls durch Fluor, Chlor, Methoxy oder Ethoxy substituiertes Acetyl, Propionyl, n- oder i-Butyroyl, Methoxycarbonyl, Ethoxycarbonyl, n- oder i-Propoxycarbonyl, Methylaminocarbonyl, Ethylammocarbonyl, n- oder i-Propylaminocarbonyl steht.R, 3 for hydrogen, for formyl, for methyl or ethyl, or for in each case optionally substituted by fluorine, chlorine, methoxy or ethoxy, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl , Ethylammocarbonyl, n- or i-propylaminocarbonyl.
4. Verbindungen gemäß Anspruch 1, dadurch gekennzeichnet, dass4. Compounds according to claim 1, characterized in that
Ar für jeweils gegebenenfalls durch Cyano, Fluor, Chlor, Brom, Methyl,Ar for each optionally by cyano, fluorine, chlorine, bromine, methyl,
Ethyl, Trifluormethyl, Methoxy, Ethoxy, Difluormethoxy, Trifluor- methoxy, Methylthio, Ethylthio, Difluormethylthio, Trifluormethyl- thio, Methylsulfmyl, Ethylsulfinyl, Trifluormethylsulfinyl, Methylsulfonyl, Ethylsulfonyl, Trifluormethylsulfonyl, Methoxycarbonyl oder Ethoxycarbonyl substituiertes Phenyl oder Thienyl steht,Ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, difluoromethylthio, trifluoromethylthio, methylsulfmyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoromethyloxyylyl, ethyl or trifluoromethylcarbonyl
R1 für jeweils gegebenenfalls durch Fluor, Chlor, Brom, Methoxy,R 1 for each optionally by fluorine, chlorine, bromine, methoxy,
Ethoxy, Methylthio, Ethylthio, Methylsulfmyl, Ethylsulfinyl, Methylsulfonyl oder Ethylsulfonyl substituiertes Methyl, Ethyl, n-, i- oder cyclo-Propyl steht,Ethoxy, methylthio, ethylthio, methylsulfmyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl is substituted methyl, ethyl, n-, i- or cyclopropyl,
R2 für Wasserstoff steht und R3 für Wasserstoff, für Formyl, für jeweils gegebenenfalls durch Fluor, Chlor, Methoxy oder Ethoxy substituiertes Acetyl, Propionyl, n- oder i-Butyroyl, Methoxycarbonyl, Ethoxycarbonyl, n- oder i-Propoxycarbonyl, oder für Phenylcarbonyl steht.R 2 represents hydrogen and R 3 represents hydrogen, formyl, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, optionally substituted by fluorine, chlorine, methoxy or ethoxy, or phenylcarbonyl.
5. Verfahren zum Herstellen von Verbindungen gemäß Anspruch 1, dadurch gekennzeichnet, dass5. A method for producing connections according to claim 1, characterized in that
Biguanide der allgemeinen Formel (II),Biguanides of the general formula (II),
Figure imgf000048_0001
in welcher
Figure imgf000048_0001
in which
Ar, R2 und R3 die oben angegebene Bedeutung haben,Ar, R 2 and R 3 have the meaning given above,
- und/oder Säureaddukte von Verbindungen der allgemeinen Formel (II)and / or acid adducts of compounds of the general formula (II)
mit Alkoxycarbonylverbindungen der allgemeinen Formel (III) R'-CO-OR' (III)with alkoxycarbonyl compounds of the general formula (III) R'-CO-OR '(III)
in welcherin which
R die oben angegebene Bedeutung hat undR has the meaning given above and
R' für Alkyl steht,R 'represents alkyl,
gegebenenfalls in Gegenwart eines Reaktionshilfsmittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels umgesetzt werden und gegebenenfalls an den so erhaltenen Verbindungen der allgemeinen Formel (I) im Rahmen der Substituentendefinition weitere Umwandlungen nach üblichen Methoden durchgeführt werden.if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent and, if appropriate, further conversions are carried out on the compounds of the general formula (I) thus obtained as part of the definition of the substituent by customary methods.
6. Verfahren zum Bekämpfen von unerwünschtem Pflanzenwuchs oder tierischen Schädlingen, dadurch gekennzeichnet, dass man mindestens eine Verbindung gemäß einem der Ansprüche 1 bis 4 auf unerwünschte Pflanzen, die tierische Schädlinge und/oder ihren Lebensraum einwirken läßt.6. A method for controlling unwanted plant growth or animal pests, characterized in that at least one compound according to one of claims 1 to 4 is allowed to act on undesired plants, the animal pests and / or their habitat.
7. Verwendung von mindestens einer Verbindung gemäß einem der Ansprüche7. Use of at least one compound according to one of the claims
1 bis 4 zum Bekämpfen von unerwünschten Pflanzen und oder tierischen Schädlingen.1 to 4 for controlling unwanted plants and or animal pests.
8. Mittel, gekennzeichnet durch einen Gehalt an einer Verbindung gemäß einem der Ansprüche 1 bis 4 und üblichen Streckmitteln und/oder oberflächenaktiven Mitteln.8. Composition, characterized by a content of a compound according to one of claims 1 to 4 and conventional extenders and / or surface-active agents.
9. Verfahren zum Herstellen von Mitteln, dadurch gekennzeichnet, dass man eine Verbindung gemäß einem der Ansprüche 1 bis 4 mit üblichen Streck- mittein und oder oberflächenaktiven Mitteln vermischt.9. A process for the preparation of agents, characterized in that a compound according to any one of claims 1 to 4 is mixed with conventional extenders and or surface-active agents.
10. Verbindungen der allgemeinen Formel (II),10. Compounds of the general formula (II),
1 , 1 I1, 1 I
R3 H H in welcherR 3 HH in which
Ar, R )2 und J τ R>3 die in Anspruch 1 angegebene Bedeutung haben. Ar, R) 2 and J τ R> 3 have the meaning given in claim 1.
PCT/EP2001/002439 2000-03-16 2001-03-05 Substituted 1-aryl-cyclopropylmethylamino-1,3,5-triazines WO2001068616A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001248330A AU2001248330A1 (en) 2000-03-16 2001-03-05 Substituted 1-aryl-cyclopropylmethylamino-1,3,5-triazines

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10012820.3 2000-03-16
DE2000112820 DE10012820A1 (en) 2000-03-16 2000-03-16 New N2-(cyclopropyl-aryl-methyl)-1,3,5-triazine-2,4-diamine derivatives useful as pre- or post-emergence, total or selective herbicides or as pesticides, e.g. insecticides

Publications (1)

Publication Number Publication Date
WO2001068616A1 true WO2001068616A1 (en) 2001-09-20

Family

ID=7634951

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2001/002439 WO2001068616A1 (en) 2000-03-16 2001-03-05 Substituted 1-aryl-cyclopropylmethylamino-1,3,5-triazines

Country Status (4)

Country Link
AR (1) AR027974A1 (en)
AU (1) AU2001248330A1 (en)
DE (1) DE10012820A1 (en)
WO (1) WO2001068616A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002094802A1 (en) * 2001-05-22 2002-11-28 Grünenthal GmbH Substituted c-furan-2-yl-methylamine and c-thiophen-2-yl-methylamine derivatives
WO2024022502A1 (en) * 2022-07-29 2024-02-01 江西天宇化工有限公司 α-SUBSTITUTED BENZYL-TRIAZINE COMPOUND, PREPARATION METHOD THEREFOR, USE THEREOF, AND HERBICIDE

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3830810A (en) * 1971-12-01 1974-08-20 Ciba Geigy Corp S-triazine derivatives
DE19641692A1 (en) * 1996-10-10 1998-04-23 Bayer Ag Substituted 2,4-diamino-1,3,5-triazines
DE19925329A1 (en) * 1998-06-16 1999-12-23 Hoechst Schering Agrevo Gmbh New triazine derivatives useful as selective herbicides and plant growth regulators
WO2001010849A2 (en) * 1999-08-04 2001-02-15 Bayer Aktiengesellschaft Substituted arylalkylamino-1,3,5-triazines as herbicides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3830810A (en) * 1971-12-01 1974-08-20 Ciba Geigy Corp S-triazine derivatives
DE19641692A1 (en) * 1996-10-10 1998-04-23 Bayer Ag Substituted 2,4-diamino-1,3,5-triazines
DE19925329A1 (en) * 1998-06-16 1999-12-23 Hoechst Schering Agrevo Gmbh New triazine derivatives useful as selective herbicides and plant growth regulators
WO2001010849A2 (en) * 1999-08-04 2001-02-15 Bayer Aktiengesellschaft Substituted arylalkylamino-1,3,5-triazines as herbicides

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002094802A1 (en) * 2001-05-22 2002-11-28 Grünenthal GmbH Substituted c-furan-2-yl-methylamine and c-thiophen-2-yl-methylamine derivatives
US6878740B2 (en) 2001-05-22 2005-04-12 Gruenenthal Gmbh Substituted C-furan-2-yl-methylamine and C-thiophen-2-yl-methylamine compounds
WO2024022502A1 (en) * 2022-07-29 2024-02-01 江西天宇化工有限公司 α-SUBSTITUTED BENZYL-TRIAZINE COMPOUND, PREPARATION METHOD THEREFOR, USE THEREOF, AND HERBICIDE

Also Published As

Publication number Publication date
AR027974A1 (en) 2003-04-23
AU2001248330A1 (en) 2001-09-24
DE10012820A1 (en) 2001-09-20

Similar Documents

Publication Publication Date Title
WO2004067518A1 (en) Substituted pyrimidines
DE10000600A1 (en) New N-substituted oxazolyl-uracil and thiazolyl-uracil derivatives useful as herbicides, especially for weed control in crops
WO2002081473A1 (en) Substituted azoloazin(thi)ones
WO2001090071A2 (en) Substituted iminoazines used as herbicides
WO2002006244A1 (en) Heterocyclic substituted herbicidal sulphonic acid anilides
EP1373228A1 (en) Substituted fluoroalcoxyphenylsulfonylurea
WO2001091558A1 (en) Herbicidal agents based on substituted carboxamides
WO2001090102A2 (en) 6-heterocyclyl-3-oxo-3,4-dihydro-quinoxalines
WO2001066527A1 (en) Substituted benzoylcyclohexenones
WO2001047894A1 (en) Substituted benzoylcyclohexane diones for use as herbicides
WO2001010861A2 (en) Substituted heterocyclyl-2h-chromenes
WO2002010160A2 (en) Substituted heterocyclyl alkylamino-1,3,5-triazines
EP1178985A1 (en) Substituted thienocycloalk(en)ylamino-1,3,5-triazine
WO2001010849A2 (en) Substituted arylalkylamino-1,3,5-triazines as herbicides
WO2001023356A1 (en) Substituted n-phenyl-phenoxy nicotinic acid-(thio) amides and their use as herbicides
WO2001068616A1 (en) Substituted 1-aryl-cyclopropylmethylamino-1,3,5-triazines
WO2001010853A1 (en) Substituted 2-imino-thiazolines
EP1204651B1 (en) Herbicidal 5-chlorodifluoromethyl-1,3,4-thiadiazol-2-yl-oxyacetanilides
WO2002020487A1 (en) Substituted 1-aryl-pyridin-2-(thi)ones
WO2003006461A1 (en) Substituted benzo-nitro-heterocycles
EP1322639A1 (en) Substituted aryl ketones and their use as herbicides
WO2003070696A2 (en) Substituted aryl ketones
WO2001005786A2 (en) Use of optically active thienylalkylamino-1,3,5-triazines as herbicides
WO2001010862A2 (en) Substituted heterocyclybenzofuranes
EP1501360A1 (en) 2,6 substituted pyridine-3-carbonyl derivatives serving as plant protection agents having herbicidal action

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP