KR20020005008A - Substituted N-cyano-amidines - Google Patents

Abstract

The present invention relates to novel substituted N-cyano-amidines of general formula (I), methods for their preparation and their use as herbicides:

Where

R ¹ represents hydrogen or in each case optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl or arylalkyl,

R ² in each case represents benzo-fused, pyrido-fused or thieno-fused cycloalk (en) yl, oxacycloalk (en) yl or thiacycloalk (en) yl, wherein all Click or heterocyclic groups may be substituted.

Description

Substituted N-cyano-amidines

It is already known that certain substituted N-cyano-guanidines have herbicidal properties (see DE-A-2505301, US-A-4661520, US-A-4684398, US-A-4689348, J. Agric). Food Chem. 37 (1989), 809-814. However, the properties of the various aspects of the preceding substituted N-cyano-guanidines do not meet the high requirements for modern crop processing agents.

The present invention relates to novel substituted N-cyano-amidines, methods for their preparation and their use as herbicides.

The present invention provides novel substituted N-cyano-amidines of the general formula (I):

Where

R ¹ represents hydrogen or in each case optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl or arylalkyl,

R ² in each case represents benzo-fused, pyrido-fused or thieno-fused cycloalk (en) yl, oxacycloalk (en) yl or thiacycloalk (en) yl, wherein all Click or heterocyclic groups may be substituted.

Formula (I) includes the possible E and Z geometric isomers in each case.

In the definition, hydrocarbon chains such as alkyl, alkenyl or alkynyl are each straight or branched chain.

Preferred substituents of the radicals listed in the formulas mentioned above or below are described below.

R ¹ preferably represents hydrogen or optionally cyano-, halogen-, C ₁ -C ₄ -alkoxy-, C ₁ -C ₄ -alkylthio-, C ₁ -C ₄ -alkylsulfinyl- or C _1- C ₄ -alkylsulfonyl-substituted and alkyl having 1 to 6 carbon atoms, in each case optionally halogen-substituted and in each case alkenyl or alkynyl having 2 to 6 carbon atoms, In each case a cycloalkyl group having from 3 to 6 carbon atoms and optionally 1 to 4 carbon atoms at the alkyl moiety and optionally in each case a cyano-, halogen- or C ₁ -C ₄ -alkyl substituted cycloalkyl or cycloalkyl Alkyl, or in each case 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl moiety and optionally in each case nitro-, cyano-, halogen-, C ₁ -C ₄ -alkyl -, C ₁ -C ₄ - halogenoalkyl -, C ₁ -C ₄ - alkoxy - or C ₁ -C ₄ - Halogenoalkoxy-substituted aryl or arylalkyl.

R ² is preferably in each case a benzo-fused, pyrido-fused or thieno-fused cycloalk (en) yl, oxacycloalk (en) yl or thiacycloalk (en) selected from the following list Indicates work;

Wherein all cyclic or heterocyclic groups may be substituted by substituents preferably selected from the groups listed below:

Nitro, hydroxy, amino, cyano, carbamoyl, thiocarbamoyl, formylamino, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -halogenoalkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -halogenoalkylthio, C ₁ -C ₄ -alkylsulfinyl, C ₁ -C ₄ -halogenoalkylsulfinyl , C ₁ -C ₄ -alkylsulfonyl, C ₁ -C ₄ -halogenoalkylsulfonyl, C ₁ -C ₄ -alkylamino, di- (C ₁ -C ₄ -alkyl) -amino, C ₁ -C ₄ -alkyl-carbonyl, C ₁ -C ₄ -alkoxy-carbonyl, C ₁ -C ₄ -alkylamino-carbonyl, di- (C ₁ -C ₄ -alkyl) -amino-carbonyl, C _1- C ₄ -alkyl-carbonyl-amino, C ₁ -C ₄ -alkoxy-carbonyl-amino, C ₁ -C ₄ -alkyl-amino-carbonyl-amino, C ₁ -C ₄ -alkyl-sulfonyl-amino .

R ¹ particularly preferably represents hydrogen, or in each case optionally cyano-, fluorine-, chlorine-, bromine-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-, Ethylthio-, n- or i-propylthio-, methylsulfinyl-, ethylsulfinyl-, n- or i-propylsulfinyl-, methylsulfonyl-, ethylsulfonyl-, n- or i-propylsul Phenyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or in each case optionally fluorine-, chlorine- or bromine-substituted ethenyl, propenyl Cyclopropyl, butenyl, ethynyl, propynyl or butynyl, or in each case optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-substituted cyclopropyl , Cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, or in each case optionally nitro-, -, Fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, Oxy-, n- or i-propoxy-, difluoromethoxy- or trifluoromethoxy-substituted phenyl or benzyl.

R ² particularly preferably represents one of the aforementioned cyclic and heterocyclic groups which may be substituted by substituents selected from the groups listed below:

Nitro, hydroxy, amino, cyano, carbamoyl, thiocarbamoyl, formylamino, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl , Difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoro Methoxy, chlorodifluoromethoxy, fluorodichloromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, fluoro Dichloromethylthio, methylsulfinyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl, methylamino, ethylamino, n- or i-propylamino, dimethylamino , Diethylamino, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl, dimethylaminocarbonyl , Diethylaminocarbonyl, acetylamino, propionylamino, n- or i-butyroylamino, methoxycarbonylamino, ethoxycarbonylamino, n- or i-propoxycarbonylamino, methylaminocarbon Carbonylamino, ethylaminocarbonylamino, n- or i-propylaminocarbonylamino, methylsulfonylamino, ethylsulfonylamino, n- or i-propylsulfonylamino.

R ¹ very particularly preferably represents hydrogen or in each case optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-, ethylthio -Methylsulfinyl-, ethylsulfinyl-, methylsulfonyl-, ethylsulfonyl-substituted methyl, ethyl, n- or i-propyl.

R ² very particularly preferably represents benzo-fused cycloalk (en) yl selected from the following list;

Wherein all cyclic groups may be substituted by substituents selected from the groups listed above.

R ¹ most preferably represents hydrogen, methyl, ethyl, n- or i-propyl.

R ² most preferably represents any of the following groups:

Preferred compounds according to the invention are given by compounds of the general formula (I) which comprise a combination of the meanings defined above as preferred.

Particularly preferred compounds according to the invention are represented by compounds of the general formula (I) which comprise a combination of the meanings defined above as particularly preferred.

Very particularly preferred compounds according to the invention are represented by compounds of the general formula (I) which comprise a combination of the meanings defined above as very particularly preferred.

Most preferred compounds according to the invention are represented by compounds of the general formula (I) comprising a combination of meanings defined as the most preferred above.

The general or preferred radical definitions mentioned above apply to the final product of general formula (I) and also correspondingly to the starting materials or intermediates necessary in each case for preparation. These radical definitions may be combined with one another as desired, ie including combinations between given preferred ranges.

Newly substituted N-cyano-amidines of formula (I) have useful biological properties. In particular, this compound has potent herbicidal activity.

Newly substituted N-cyano-amidines of formula (I) are

The following N-cyano-imidates of formula (II) are obtained by reacting with amino compounds of formula (III) in the presence of a reaction aid, if appropriate, and in the presence of a diluent, if appropriate:

Where

R ¹ and R ² are each as defined above,

R 'represents alkyl.

For example, when using ethyl N-cyano-propaneimidate and indan-2-yl-amine as starting materials, the reaction process in the process according to the invention can be represented by the following scheme:

Formula (II) provides a general definition of N-cyano-imidate used as starting material in the process according to the invention for the preparation of compounds of formula (I). In formula (II), R ¹ is preferably already mentioned as preferred, particularly preferred as very particularly preferred or most preferred as R ¹ with respect to the description of the compounds of formula (I) according to the invention. Have meaning; R 'represents alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl.

N-cyano-imidates of formula (II) can be prepared by known and / or known methods per se (J. Am. Chem. Soc. 104 (1982), 235-239; loc cit. 106 (1984), 2805-2811; J. Org.Chem. 28 (1963), 1816-1821; loc.cit. 46 (1981), 1457-1465; Synthesis 1983, 402-404; Tetrahedron Lett. 21 (1980), 909-912).

Formula (III) provides a general definition of amino compounds which are also used as starting materials in the process according to the invention for the preparation of compounds of formula (I). In formula (III), R ² is already mentioned as preferred, particularly preferred, very particularly preferred or most preferred as regards R ² with respect to the description of the compounds of formula (I) according to the invention. Has a meaning.

Amino compounds of formula (III) can be prepared by methods known and / or known per se (J. Am. Chem. Soc. 88 (1966), 2233-2240; loc. Cit. 95 ( 1973), 4083-4084; J. Am. Chem. Soc. C 1966, 717-722; Synthesis 1980, 695-697; Tetrahedron 24 (1968), 3681-3696; loc.cit. 50 (1994), 3627- 3638).

The process according to the invention for the preparation of compounds of general formula (I) is carried out using reaction aids as appropriate. Suitable reaction aids for carrying out the process according to the invention are generally customary inorganic or organic base or acid acceptors. These preferably include alkali or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrogenates, hydroxides or alkoxides, such as sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, Sodium carbonate, potassium carbonate or calcium carbonate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide or potassium methoxide, sodium ethoxide Seed or potassium ethoxide, sodium n- or i-propoxide or potassium n- or i-propoxide, sodium n-, i-, s- or t-butoxide or potassium n-, i-, s- Or t-butoxide; Basic organic nitrogen compounds such as trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N, N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexyl Amine, N, N-dimethyl-aniline, N, N-dimethylbenzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3 , 4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo [2,2 , 2] -octane (DABCO), 1,5-diazabicyclo [4,3,0] -non-5-ene (DBN) or 1,8-diazabicyclo [5,4,0] -undec- 7-yen (DBU) is included.

In most cases, it can be done without using any of the above mentioned reaction aids.

The process according to the invention for the preparation of compounds of general formula (I) is preferably carried out using diluents. Suitable diluents are especially inert organic solvents besides water. These include, inter alia, optionally halogenated aliphatic, cycloaliphatic and aromatic hydrocarbons, such as benzine, 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 ether or ethylene glycol 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 monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; Water or purified water and mixtures thereof.

When carrying out the process according to the invention, the reaction temperature can be varied within a significant range. In general, the reaction is carried out at temperatures between 0 and 150 ° C., preferably between 10 and 120 ° C.

The process according to the invention is generally carried out at atmospheric pressure. However, it is also possible for the process according to the invention to be carried out at elevated or reduced pressure, generally between 0.1 and 10 bar.

When carrying out the process according to the invention, the starting materials are generally used in almost equimolar amounts. However, one of the components may also use a relatively excess amount. The reaction is generally carried out in a suitable diluent in the presence of a reaction aid, if appropriate, and the reaction mixture is generally stirred for a long time at the required temperature. Post-treatment of the reaction is carried out by conventional methods (see Preparation Examples).

The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular weed killer. Weeds in the broad sense mean all plants that grow in unwanted places. Whether the material according to the invention acts as a total or selective herbicide depends essentially on the amount used.

The active compounds according to the invention can be used, for example, in connection with the following plants:

Dicotyledonous weeds in the genus

Sina piece (Sinapis), Les pidyum (Lepidium), gallium (Galium), Stella Ria (Stellaria), Mart Rica Ria (Matricaria), Ante Miss (Anthemis), the ground cattle (Galinsoga), Ke-established, Rhodium (Chenopodium), Urtica , Senecio , Amaranthus , Portulaca , Xanthium , Convolvulus , Ipomoea , Polygonum , Seth Vania (Sesbania), Ambrosia (Ambrosia), unsealing syum (Cirsium), carboxylic Douce (Carduus), hand kusu (Sonchus), Solar num (Solanum), roripa (Rorippa), in Tallahassee (Rotala), Lin der California ( Lindernia), La hated (Lamium), Veronica (Veronica), Abu epothilone (Abutilon), the Mex (Emex), Datura (Datura), viola (viola), Gale option system (Galeopsis), Papa Bell (Papaver), Centaurea , Trifolium , Ranunculus and Taraxacum .

Dicotyledonous crops of the genus

Notice europium (Gossypium), glycidyl cine (Glycine), Beta (Beta), Dow kusu (Daucus), Pace come loose (Phaseolus), pisum (Pisum), Solar num (Solanum), rinum (Linum), epoch Moe O ( Ipomoea , Vicia , Nicotiana , Lycopersicon , Arachis , Brassica , Lactuca , Cucumis and Cucurbita ( Cucurbita ).

Monocotyledonous weeds in the genus

Echinochloa , Setaria , Panicum , Digitaria , Phleum , Poa , Festuca , Eleusin , Brachiaria , Lolium , Bromus , Avena , Cyperus , Sorghum , Agropyron , Cynodon , Mono Korea, Monochoria , Fimbristylis , Sagittaria , Eleocharis , Scirpus , Paspalum , Iscamum , Spenoclea Sphenoclea), daktil'll help Locke (Dactyloctenium), Agrobacterium seutiseu (Agrostis), Alor page kuruseu (Alopecurus), ahpera (Apera), Ah way rope switch (Aegilops) or Palazzo lease (Phalaris) on.

Monocotyledonous crops of the genus

Duck Party (Oryza), Jea (Zea), tree tikum (Triticum), Johor deum (Hordeum), ABE or (Avena), three-Calais (Secale), sorbitol gum (Sorghum), Trapani Qom (Panicum), Saccharomyces Room ( Saccharum), Ananas (Ananas), aspartate Goose (Asparagus) and Allium (Allium).

However, the use of the active compounds according to the invention is not limited at all in the above, but extends to other plants in the same way.

The active compounds according to the invention are suitable for the overall control of weeds, depending on concentration, for example on industrial zones and railway lines, and on sidewalks and plazas with or without trees. Likewise, the active compounds according to the invention are for example forests, ornamental plantations, orchards, vineyards, citrus fields, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, palm plantations, cocoa plantations, soft fruit plantations and It can be used to control weeds from perennial crops growing on hop fields, lawns, sports fields and pastures, and to selectively control weeds from annual crops.

When applied to soil and the above-described plant cultivation, the compound of general formula (I) according to the present invention has a strong herbicidal activity and a broad spectrum of activity. To some extent these compounds are also suitable for the selective control of monocotyledonous or dicotyledonous weeds both before and after germination in monocotyledonous and dicotyledonous crops.

Active compounds include solutions, emulsions, hydrating powders, suspensions, powders, powders, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with the active compounds, and microcapsules in polymeric materials. It may be converted to a conventional formulation.

These formulations are prepared by known methods, for example by mixing the active compounds with extenders, ie liquid solvents and / or solid carriers, optionally using surfactants, ie emulsifiers and / or dispersants and / or foam-forming agents. .

If the extender used is water, for example an organic solvent can also be used as auxiliary solvent. Suitable liquid solvents are mainly aromatic compounds such as xylene, toluene or alkylnaphthalene; Chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride; Aliphatic hydrocarbons such as cyclohexane or paraffins such as petroleum fractions, mineral oils and vegetable oils; Alcohols such as butanol or glycols and ethers and esters thereof; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; Strong polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

Suitable solid carriers are, for example, ammonium salts and ground natural minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and highly dispersed silica, alumina And milled synthetic minerals such as silicates. Solid granules suitable for granulation include, for example, pulverized and classified natural rocks such as calcite, marble, pumice, calcite and dolomite; And synthetic granules of inorganic and organic powders; And granules of organic substances such as sawdust, coconut husks, corn cobs and tobacco. Suitable emulsifiers and / or foam-forming agents are for example nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters; Polyoxyethylene fatty alcohol ethers such as alkylaryl polyglycol ethers; Alkyl sulfonates; Alkyl sulfates; Aryl sulfonate; And proteolytic products are suitable. Dispersants are, for example, lignin-sulfite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latex, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids such as cephalin and lecithin, and synthetic phospholipids Can be used. Other possible additives are mineral and vegetable oils.

Colorants such as inorganic pigments such as iron oxide, titanium oxide and prussian blue, and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes and salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc Micronutrients can be used.

The formulations generally contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight of active compound.

To control weeds, the active compounds according to the invention can be used on their own or as a mixture with known herbicides in the form of their preparations, and finished formulations or tank mixtures can be used.

Possible components in the mixture are known herbicides such as acetochlor, acifluorfen (-sodium), acloniphene, alachlor, alkoxydim (-sodium), amethrin, amidochlor, amidosulfuron, anil Lofos, asulam, atrazine, azaphenidine, azimsulfuron, benazolin (-ethyl), benfuresate, bensulfuron (-methyl), bentazone, benzobicyclo, benzophene, benzoylprop (-ethyl ), Bialaphos, bifenox, bispyribac (-sodium), bromobutide, bromophenoxime, bromoxynil, butachlor, butoxydim, butyrate, carfenstrol, caloxydim, carbeta Mead, carfentrazone (-ethyl), chlormethoxyphene, chlorambene, chloridazone, chlorimuron (-ethyl), chlornitropen, chlorsulfuron, chlortoluron, cinidon (-ethyl), shin Methylene, cynosulfuron, clepoxydim, cletodim, clodinapop (-propargyl), clomazone, clomeprop, chlor Lallyde, clopyrasulfuron (-methyl), chloransullam (-methyl), cumyluron, cyanazine, cybutrin, cycloate, cyclosulfamuron, cyclooxydim, sihalofop (-butyl) , 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallylate, dicamba, diclofo (-methyl), diclosullam, dietathyl (-ethyl), dipfenzoku Art, Diflufenican, Diflufenzopyr, Dimefuron, Dimepiferrate, Dimethaclor, Dimethamethrin, Dimethenamid, Dimexiflom, Dinitramine, Diphenamide, Diquat, Dithiopyr, Diuron, Dimron, Eprofodan, EPTC, Esprocarb, Etalfluralin, Etamethsulfuron (-methyl), Etofumesate, Ethoxyphene, Ethoxysulfuron, Etobenzanide, Phenoxaprop (- P-ethyl), pentrazamide, flamprop (-isopropyl), flamprop (-isopropyl-L), flamprop (-methyl), plazasulfuron, florasullam, fluazipope (-P Butyl), Luazolate, flucarbazone, flufenacet, flumetsulam, flumichlorac (-pentyl), flumioxazine, flumipropine, flumetsulam, fluoromethuron, fluorochloridone, fluoroglosses Lycopene (-ethyl), flupoxam, flupropacyl, flupyrsulfuron (-methyl, -sodium), flurenol (-butyl), flulidone, fluoroxypyr (-methyl), fluprimidol, Flutamone, fluthiacet (-methyl), flutiamide, pomesaphene, glufosinate (-ammonium), glyphosate (-isopropylammonium), halosafen, haloxope (-ethoxyethyl), Haloxypope (P-methyl), hexazinone, imazamethabenz (-methyl), imazamethapir, imazamox, imazapic, imazaphyr, imazaquin, imazetapyr, imazasulfuron, iodosul Furon (-methyl, -sodium), isocinyl, isoprophalin, isoproturon, isouron, isoxaben, isoxachlortol, isoxaplutol, isoxa Pyripop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, mesotrione, metamitrone, metazachlor, metabenzthiazuron, methopenzuron, methopromurone, (alpha-) Metolachlor, methotsullam, methoxuron, metribuzin, metsulfuron (-methyl), molinate, monolinuron, naproanilide, naprofamide, neburon, nicosulfuron, norflurazon, or Benkab, oryzaline, oxadiargyl, oxadione, oxasulfuron, oxaziclomethone, oxyfluorfen, paraquat, pellagonic acid, pendimethalin, pendralline, pentoxazone, penmedipam, Piperophos, pretilachlor, primisulfuron (-methyl), promethrin, propachlor, propanyl, propaquizapov, propisochlor, propizamide, prosulfocarb, prosulfuron, pyra Flufen (-ethyl), pyrazolate, pyrazosulfuron (-ethyl), pyrazoxifen, pyribenzoxime, pyributycarb, blood REDATE, PYRIMINOBAC (-methyl), PYRIthioBAK (-SODIUM), quinclolac, quinmerac, quinoclamin, quinazolof (-P-ethyl), quinazolof (-P-tefuryl) , Rimsulfuron, cetoxydim, simazine, cymetrin, sulfotelion, sulfentrazone, sulfomethuron (-methyl), sulfosate, sulfosulfuron, tebutam, tebutiuuron, tetraproxydim, Tebutylrazine, Terbutrin, Tenylchlor, Thiafluamide, Tiazopyr, Tidiazimine, Thifensulfuron (-methyl), Thiobencarb, Thiocarbazyl, Tralcoxidim, Trialate, Triasol Furon, tribenuron (-methyl), triclopyr, tridiphane, trituralin and triflusulfuron.

Mixtures with other known active compounds such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and soil structure improvers are also possible.

The active compounds can be used on their own in the form of their formulations or in the form of further dilution prepared from them, for example in immediate-use solutions, suspensions, emulsions, powders, pastes and granules. The active compound is used by conventional methods such as, for example, watering, spraying, atomizing or scattering.

The active compounds according to the invention can be used before and after germination of plants. They can also be incorporated into the soil before sowing.

The amount of active compound can vary within a significant range. This is essentially dependent on the nature of the desired effect. Generally, the amount used is from 1 g to 10 kg, preferably from 5 g to 5 kg of active compound per hectare of soil surface.

The preparation and use of the active compounds according to the invention can be seen from the following examples.

Manufacturing Example:

Example 1

A mixture of 0.98 g (10 mmol) of methyl N-cyano-ethaneimidate, 1.42 g (10 mmol) of 1,2,3,4-tetrahydro-1-naphthylamine and 20 mL of water was added at room temperature (about 20 ° C.) Stir for 12 hours. The resulting crystalline product was then separated by suction filtration, washed with a small amount of water and diethyl ether, and then dried over a disk made of clay.

1.3 g (62% of theory) of N'-cyano-N- (1,2,3,4-tetrahydro-1-naphthyl) -ethaneimideamide at a melting point of 113 ° C were obtained.

Similar to Example 1 and according to the general description of the preparation process according to the invention, compounds of general formula (I), for example, listed in Table 1 below can be prepared.

Table 1 : Examples of Compounds of Formula (I)

Example of use

Example A

Germination test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

A suitable formulation of the active compound is prepared by mixing 1 part by weight of the active compound with the solvent in the amounts mentioned above, adding the aforementioned amount of emulsifier and then diluting the concentrate with water to the desired concentration.

Seeds of the test plants were sown in normal soil. After about 24 hours, the soil was sprayed with the active compound formulation to apply a specific amount of the desired active compound per unit area. The concentration of the spray solution was chosen such that a specific amount of the desired active compound was applied at 1000 liters of water per hectare.

After 3 weeks, the degree of damage of the plants was recorded as percent damage compared to the development of the untreated control.

The figures represent the following:

0% = no effect (same as untreated control)

100% = complete control

In this test, for example, the compound of Preparation Example 1 showed potent activity against weeds.

Example B

Post Germination Test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

A suitable formulation of the active compound is prepared by mixing 1 part by weight of the active compound with the solvent in the amounts mentioned above, adding the aforementioned amount of emulsifier and then diluting the concentrate with water to the desired concentration.

Test plants of 5 to 15 cm in height were sprayed with the active compound preparation to apply a specific amount of the desired active compound per unit area. The concentration of the spray solution was chosen such that a specific amount of the desired active compound was applied at 1000 liters of water per hectare.

After 3 weeks, the degree of damage of the plants was recorded as percent damage compared to the development of the untreated control.

The figures represent the following:

0% = no effect (same as untreated control)

100% = complete control

In this test, for example, the compound of Preparation Example 1 showed potent activity against weeds.

Claims (8)

Substituted N-cyano-amidines of Formula (I) Where R ¹ represents hydrogen or in each case optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl or arylalkyl, R ² in each case represents benzo-fused, pyrido-fused or thieno-fused cycloalk (en) yl, oxacycloalk (en) yl or thiacycloalk (en) yl, wherein all Click or heterocyclic groups may be substituted. The method of claim 1, R ¹ represents hydrogen or optionally cyano-, halogen-, C ₁ -C ₄ -alkoxy-, C ₁ -C ₄ -alkylthio-, C ₁ -C ₄ -alkylsulfinyl- or C ₁ -C ₄ -alkylsulfonyl-substituted and represent alkyl having 1 to 6 carbon atoms, in each case optionally halogen-substituted and in each case represent alkenyl or alkynyl having 2 to 6 carbon atoms, or Cycloalkyl or cycloalkylalkyl having 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl moiety and optionally in each case cyano-, halogen- or C ₁ -C ₄ -alkyl substituted Or in each case 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl moiety and optionally in each case nitro-, cyano-, halogen-, C ₁ -C ₄ -alkyl-, C ₁ -C ₄ -halogenoalkyl-, C ₁ -C ₄ -alkoxy- or C ₁ -C ₄ -halogenoalkoxy Time-substituted aryl or arylalkyl, R ² in each case represents benzo-fused, pyrido-fused or thieno-fused cycloalk (en) yl, oxacycloalk (en) yl or thiacycloalkyl (kenyl) selected from the following list; Wherein all cyclic or heterocyclic groups may be substituted by substituents preferably selected from the groups listed below, Substituents here are nitro, hydroxy, amino, cyano, carbamoyl, thiocarbamoyl, formylamino, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -Alkoxy, C ₁ -C ₄ -halogenoalkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -halogenoalkylthio, C ₁ -C ₄ -alkylsulfinyl, C ₁ -C ₄ -halo Genoalkylsulfinyl, C ₁ -C ₄ -alkylsulfonyl, C ₁ -C ₄ -halogenoalkylsulfonyl, C ₁ -C ₄ -alkylamino, di- (C ₁ -C ₄ -alkyl) -amino, C ₁ -C ₄ -alkyl-carbonyl, C ₁ -C ₄ -alkoxy-carbonyl, C ₁ -C ₄ -alkylamino-carbonyl, di- (C ₁ -C ₄ -alkyl) -amino-carbonyl , C ₁ -C ₄ -alkyl-carbonyl-amino, C ₁ -C ₄ -alkoxy-carbonyl-amino, C ₁ -C ₄ -alkyl-amino-carbonyl-amino or C ₁ -C ₄ -alkyl- A sulfonyl-amino compound. The method according to claim 1 or 2, R ¹ represents hydrogen or in each case optionally cyano-, fluorine-, chlorine-, bromine-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, n- or i-propylthio-, methylsulfinyl-, ethylsulfinyl-, n- or i-propylsulfinyl-, methylsulfonyl-, ethylsulfonyl-, n- or i-propylsulfonyl-substituted Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or in each case optionally fluorine-, chlorine- or bromine-substituted ethenyl, propenyl, butenyl, Ethynyl, propynyl or butynyl, or in each case optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-substituted cyclopropyl, cyclobutyl, Cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, or in each case optionally nitro-, cyano-, fluorine-, chlorine-, bromine Rom-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i- Propoxy-, difluoromethoxy- or trifluoromethoxy-substituted phenyl or benzyl, R ² represents one of the cyclic and heterocyclic groups mentioned in claim 1 or 2 which may be substituted by a substituent selected from the groups listed below, Substituents here are nitro, hydroxy, amino, cyano, carbamoyl, thiocarbamoyl, formylamino, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- Or t-butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluorome Methoxy, trifluoromethoxy, chlorodifluoromethoxy, fluorodichloromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethyl Thio, fluorodichloromethylthio, methylsulfinyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl, methylamino, ethylamino, n- or i-propyl Amino, dimethylamino, diethylamino, acetyl, Lopionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbon Carbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, acetylamino, propionylamino, n- or i-butyroylamino, methoxycarbonylamino, ethoxycarbonylamino, n- or i-propoxycar Carbonylamino, methylaminocarbonylamino, ethylaminocarbonylamino, n- or i-propylaminocarbonylamino, methylsulfonylamino, ethylsulfonylamino or n- or i-propylsulfonylamino . The method according to any one of claims 1 to 3, R ¹ represents hydrogen or in each case optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, methylsulfinyl -Ethylsulfinyl-, methylsulfonyl-, ethylsulfonyl-substituted methyl, ethyl, n- or i-propyl, R ² represents benzo-fused cycloalk (en) yl selected from the following list; Wherein all cyclic groups may be substituted by substituents selected from the groups listed below, Substituents here are nitro, hydroxy, amino, cyano, carbamoyl, thiocarbamoyl, formylamino, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- Or t-butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluorome Methoxy, trifluoromethoxy, chlorodifluoromethoxy, fluorodichloromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethyl Thio, fluorodichloromethylthio, methylsulfinyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl, methylamino, ethylamino, n- or i-propyl Amino, dimethylamino, diethylamino, acetyl, Lopionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbon Carbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, acetylamino, propionylamino, n- or i-butyroylamino, methoxycarbonylamino, ethoxycarbonylamino, n- or i-propoxycar Carbonylamino, methylaminocarbonylamino, ethylaminocarbonylamino, n- or i-propylaminocarbonylamino, methylsulfonylamino, ethylsulfonylamino or n- or i-propylsulfonylamino . The method according to any one of claims 1 to 4, R ¹ represents hydrogen, methyl, ethyl, n- or i-propyl, R ² represents one of the following groups: N-cyano-imidadate of formula (II) is reacted with amino compound of formula (III) in the presence of a reaction aid if appropriate and in the presence of a diluent if Method for preparing a compound according to any one of the preceding claims: Where R ¹ and R ² are each as defined in any one of claims 1 to 5, R 'represents alkyl. A herbicide composition characterized by containing at least one compound according to any one of claims 1 to 5 and a conventional bulking agent. Use of at least one compound according to any one of claims 1 to 5 for controlling unwanted plants.