DE19962931A1 - New thienylalkylamino-1,3,5-triazine derivatives are herbicides useful as defoliants, desiccants and especially weedkillers - Google Patents

Abstract

Thienylalkylamino-1,3,5-triazine derivatives are new. The thienylalkylamino-1,3,5-triazine derivatives are R-, S- or R,S-compounds of formula (I): R<1> = CH(halo)2; 2 or 3C alkyl (each optionally substituted with 1 or 2 halo); or cyclopropyl substituted with 1-3 halo; R<2> = H, or 1-3C alkyl optionally substituted with CN, halo or 1-3C alkoxy; R<3> = 1-3C alkyl, CH3CO-, C2H5CO-, n-C3H7CO-, i-C3H7CO-, 1-3C alkoxy-CO- or 1-3C alkyl-NH-CO-; R<4> = 1-4C alkyl optionally substituted with CN, halo or 1-3C alkoxy; and R<5> and R<6> = Cl or CH3. An Independent claim is also included for the preparation of compounds (I).

Description

The invention relates to new substituted thienylalkylamino-1,3,5-triazines, processes for their preparation and their use as herbicides.

A number of thienylalkylamino-1,3,5-triazines are already from the (patent) - Literature known (see JP-A-63222166 - cited in Chem. Abstracts 111: 97288w, WO-A-98/15537, WO-A-98/15538, WO-A-98/15539, WO-A-99/18100). This ver However, bonds have not yet gained any special significance.

The new substituted thienylalkylamino-1,3,5-triazines of the general formula (I)

in which
R ¹ for dihalomethyl, ethyl, haloethyl, dihaloethyl, n-propyl, halo-n-propyl, dihalo-n-propyl, i-propyl, halo-i-propyl, dihalo-i-propyl, halocyclopropyl, dihalogenocyclopropyl or trihalocyclopropyl stands,
R ^{2 represents} hydrogen or represents methyl, ethyl, n- or i-propyl which is optionally substituted by cyano, halogen, methoxy, ethoxy, n- or i-propoxy,
R ³ for hydrogen, for formyl or for methyl, ethyl, n- or i-propyl, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, optionally substituted by cyano, halogen, methoxy, ethoxy, n- or i-propoxy , Ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, ethyl aminocarbonyl, n- or i-propylaminocarbonyl,
R ⁴ represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each optionally substituted by cyano, halogen, methoxy, ethoxy, n- or i-propoxy,
R ^{5 represents} chlorine or methyl and
R ^{6 represents} chlorine or methyl,
wherein the substituents on the carbon atom to which R ^{4 is} bonded are essentially either in the R configuration or in the S configuration, and also the respective racemates found.

If R ^{1 stands} for a substituent with an asymmetrically substituted carbon atom, both the respective possible diastereomer mixtures and the individual possible diastereomers are the subject of the invention.

Preferred substituents or ranges of those listed above and below Residues present formulas are described below.

R ¹ preferably represents difluoromethyl, dichloromethyl, dibromomethyl, chlorofluoromethyl, chlorobromomethyl, fluorobromomethyl, ethyl, fluoroethyl, chloroethyl, bromoethyl, difluoroethyl, dichloroethyl, dibromethyl, chlorofluoromethyl, bromofluoromethyl, n-propyl, fluoro-n-propyl, chloro-n -propyl, bromo-n-propyl, difluoro-n-propyl, dichloro-n-propyl, i-propyl, fluoro-i-propyl, chloro-i-propyl, bromo-i-propyl, difluoro-i-propyl, dichloro -i-propyl, fluorocyclopropyl, chlorocyclopropyl, difluorocyclopropyl, dichlorocyclopropyl, trifluorocyclopropyl, tri chlorocyclopropyl, chlorodifluorocyclopropyl or fluorodichlorocyclopropyl.
R ² preferably represents hydrogen or methyl or ethyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy.
R ³ preferably represents hydrogen, formyl or methyl, ethyl, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, which are each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy , Methylaminocarbonyl, ethylamino carbonyl, n- or i-propylaminocarbonyl.
R ⁴ preferably represents methyl, ethyl, n- or i-propyl which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy.
R ⁵ preferably represents chlorine or methyl.
R ⁶ preferably represents chlorine or methyl.
R ¹ particularly preferably represents difluoromethyl, dichloromethyl, dibromomethyl, chlorofluoromethyl, ethyl, 1-fluoro-ethyl, 2-fluoro-ethyl, 1-chloro-ethyl, 2-chloroethyl, 1-bromo-ethyl, 2-bromo-ethyl , 1,1-difluoro-ethyl, 1,2-difluoro-ethyl, 2,2-difluoro-ethyl, 1,1-dichloro-ethyl, 1,2-dichloro-ethyl, 2,2-dichloro-ethyl, 1 , 2-Di bromo-ethyl, 1-chloro-1-fluoroethyl, 1-chloro-2-fluoroethyl, 2-chloro-1-fluoroethyl, 2-chloro-2-fluoroethyl, 1-fluoro-n -propyl, 2-fluoro-n-propyl, 1-chloro-n-propyl, 2-chloro-n-propyl, 1-bromo-n-propyl, 2-bromo-n-propyl, 1-fluoro-i-propyl , 1-chloro-i-propyl, difluorocyclopropyl or dichlorocyclopropyl.
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.
R ⁴ particularly preferably represents methyl, ethyl, n- or i-propyl which is optionally substituted by fluorine, chlorine, methoxy or ethoxy.
R ⁵ particularly preferably represents chlorine or methyl.
R ⁶ particularly preferably represents chlorine or methyl.
R ¹ very particularly preferably represents difluoromethyl, dichloromethyl, chlorofluoromethyl, ethyl, 1-fluoro-ethyl, 1-chloro-ethyl, 1,1-difluoro-ethyl, 1,2-difluoro-ethyl, 1,1-dichloro-ethyl , 1,2-dichloroethyl, 1-chloro-1-fluoroethyl, 1-chloro-2-fluoroethyl, 2-chloro-1-fluoroethyl, 1-fluoro-n-propyl, 1-chloro-n -propyl, 1-fluoro-i-propyl or 1-chloro-i-propyl.
R ² very particularly preferably represents hydrogen.
R ³ very particularly preferably represents hydrogen, formyl or acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl which is optionally substituted by fluorine, chlorine, methoxy or ethoxy.
R ⁴ very particularly preferably represents methyl, ethyl, n- or i-propyl which is optionally substituted by fluorine or chlorine.
R ⁵ very particularly preferably represents chlorine.
R ⁶ particularly preferably represents methyl.

The radicals listed above or listed in preferred areas definitions apply both to the end products of the formula (I) and correspondingly for the starting or intermediate products required for the production. This Residual definitions can be between themselves, that is, between the specified ones areas can be combined as required.

Those compounds of the formula (I) are preferred according to the invention which is a combination of the meanings listed above as preferred is present.

According to the invention, particular preference is given to those compounds of the formula (I) in which a combination of those listed as particularly preferred above Meanings exist.

According to the invention, those compounds of the Formula (I), in which a combination of the above is particularly preferred added listed meanings is present.

The new substituted thienylalkylamino-1,3,5-triazines of the general formula (I) have interesting biological properties. They stand out in particular from strong herbicidal activity.

The substituted thienylalkylamino-1,3,5-triazines of the general formula (I) are obtained if biguanides of the general formula (II)

in which
R ² , R ³ , R ⁴ , R ⁵ and R ^{6 have} the meaning given above,
and / or acid adducts of compounds of the general formula (II)
with alkoxycarbonyl compounds of the general formula (III)

R ¹ -CO-OR '(III)

in which
R ^{1 has} the meaning given above and
R 'represents alkyl,
if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,
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.

If, for example, 1- (5-chloro-4-methyl-thien-2-yl-propyl) -biguanide and 2-fluoro-propanoic acid methyl ester are used as starting materials, the course of the reaction in the process according to the invention can be outlined using the following formula:

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), R ² , R ³ , R ⁴ , R ⁵ and R ⁶ preferably or in particular have those meanings which have preferably been described above in connection with the description of the compounds of the general formula (I) according to the invention or have been given as being particularly preferred for R ² , R ³ , R ⁴ , R ⁵ and R ⁶ .

Suitable acid adducts of compounds of the formula (II) are their additions products with protonic acids, such as B. with hydrogen chloride (hydrogen chloride), Hydrogen bromide (hydrogen bromide), sulfuric acid, methanesulfonic acid, benzene sulfonic acid and p-toluenesulfonic acid.

The starting materials of the general formula (II) are known and / or can be according to processes known per se (cf. JP-A-63222166, WO-A-99/18100).

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 ⁴ preferably or in particular has the meanings which have been given above or in connection with the description of the compounds of the general formula (I) according to the invention preferably or as particularly preferred for R ³ ; 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 synthesis chemicals.

The process according to the invention for the preparation of the compounds of the general Formula (I) is preferably carried out using a diluent leads. As a diluent for carrying out the method according to the invention In addition to water, inert organic solvents are particularly suitable. These include in particular aliphatic, alicyclic or aromatic, given if halogenated hydrocarbons, such as 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, propio nitrile or butyronitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacet amide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric acid triamid; 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 mono methyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

As reaction aids for the process according to the invention generally come mean the usual inorganic or organic bases or acid acceptors in Consideration. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkanolates, such as for example sodium, potassium or calcium acetate, lithium, sodium, potassium or calcium amide, sodium, potassium or calcium carbonate, sodium, potassium or calcium hydrogen carbonate, lithium, sodium, potassium or calcium hydride, Lithium, sodium, potassium or calcium hydroxide, sodium or potassium - - methanolate, ethanolate, -n- or -i-propanolate, -n-, -i-, -s- or -t-butanolate; Farther also basic organic nitrogen compounds, such as trimethylamine,  Triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N, N-dimethyl cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N, N-dimethyl-aniline, N, N-dimethyl-benzylamine, pyridine, 2-methyl, 3-methyl, 4-methyl, 2,4-di methyl, 2,6-dimethyl, 3,4-dimethyl and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl pyridine, 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-enes (DBU).

The reaction temperatures can be carried out when carrying out the process according to the invention Process can be varied over a wide range. Generally you work at 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 leads. However, it is also possible to increase the process according to the invention or reduced pressure - generally between 0.1 bar and 10 bar to lead.

To carry out the process according to the invention, the starting materials in 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 were carried out a reaction auxiliary and the reaction mixture is in space agitated several hours at the required temperature. The on work is carried out according to customary methods (cf. games).

The active compounds according to the invention can be used as defoliants, desiccants, kraut tabs killers and especially used as a weed killer. Weeds in the broadest sense are understood to mean all plants that are found in places  grow where they are undesirable. Whether the substances according to the invention as total or Selective herbicides act essentially depends on the amount used.

The active compounds according to the invention can, for. B. used in the following plants:
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, Gupopsisia, Euphorbia , Gaijum, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsesbania, Senecio , Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.

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, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.

Monocot cultures of the genera: Allium, Pineapple, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea.  

However, the use of the active compounds according to the invention is by no means limited to these Limited genres, but extends in the same way to others Plants.

According to the invention, all plants and parts of plants can be treated. Under Plants are understood here as all plants and plant populations desired and undesirable wild plants or crops (including naturally occurring crops). Cultivated plants can be plants that through conventional breeding and optimization methods through through biotechnological and genetic engineering methods or combinations of these Methods can be obtained, including transgenic plants and including those that can or cannot be protected by plant variety rights Plant varieties. Under plant parts, all above-ground and underground Parts and organs of plants, such as shoot, leaf, flower and root understood with leaves, needles, stems, stems, flowers, fruiting bodies, Fruits and seeds as well as roots, tubers and rhizomes are listed. To the Plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.

The treatment of plants and parts of plants according to the invention with the Active substances take place directly or by influencing their environment, living space or storage room according to the usual treatment methods, e.g. B. by diving, Spraying, vaporizing, atomizing, scattering, spreading and when propagating material, especially in the case of seeds, continues with one or more layers Envelop.

The active compounds according to the invention are suitable depending on the con center for total weed control, e.g. B. on industrial and track systems and on Because of and places with and without tree cover. Likewise, the fiction active agents for weed control in permanent crops, e.g. B. Forst, 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 areas and for selective weed control in annual crops become.

The compounds of formula (I) according to the invention show strong herbicidal activity solvency and a wide range of effects when used on and on the floor aerial parts of plants. To a certain extent, they are also suitable for selective use Control of monocot and dicot weeds in monocot and di cotyledon cultures, both pre-emergence and post-emergence.

The active ingredients can be converted into the usual formulations, such as Solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient im impregnated natural and synthetic materials as well as very fine encapsulation in polymers Fabrics.

These formulations are prepared in a known manner, e.g. B. by Ver mixing the active ingredients with extenders, i.e. liquid solvents and / or solid carriers, optionally using surface-active agents Agents, ie emulsifiers and / or dispersants and / or foam generating means.

In the case of the use of water as an extender, e.g. B. also organic Solvents are used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or alkyl naphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as Chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. 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.  

As solid carriers come into question: B. ammonium salts and natural Rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, Mont morillonite or diatomaceous earth and synthetic rock powder, such as highly disperse Silicic acid, aluminum oxide and silicates, as solid carriers for granules come into question: z. B. broken and fractionated natural rocks such as calcite, Marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, Coconut shells, corn cobs and tobacco stems; as emulsifying and / or foam Generating funds are possible: z. B. non-ionic and anionic Emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol Ethers, e.g. B. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates as well as protein hydrolyzates; as dispersants come into question: z. B. Lignin sulfite leach and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural, can be used in the formulations and synthetic powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospho lipids such as cephalins and lecithins and synthetic phospholipids. Further Additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferro cyan and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, Molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90%.  

The active compounds according to the invention can be used as such or in their formulations also used in a mixture with known herbicides for weed control find, where ready formulations or tank mixes are possible.

Known herbicides are suitable for the mixtures, for example Acetochlor, acifluorfen (-sodium), aclonifen, alachlor, alloxydim (-sodium), Ametryne, Amidochlor, Amidosulfuron, Anilofos, Asulam, Atrazine, Azafenidin, Azimsulfuron, benazolin (-ethyl), benfuresate, bensulfuron (-methyl), bentazone, Benzobicyclone, Benzofenap, Benzoylprop (-ethyl), Bialaphos, Bifenox, Bispyribac (- sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butroxydim, Butylates, Cafenstrole, Caloxydim, Carbetamide, Carfentrazone (-ethyl), Chlo methoxyfen, chloramben, chloridazon, chlorimuron (-ethyl), chloronitrofen, chlorine sulfuron, chlorotoluron, cinidon (-ethyl), cinmethylin, cinosulfuron, clefoxydim, Clethodim, Clodinafop (-propargyl), Clomazone, Clomeprop, Clopyralid, Clopyra sulfuron (methyl), chlorosulam (methyl), cumyluron, cyanazine, cybutryne, Cycloate, cyclosulfamuron, cycloxydim, cyhalofop (-butyl), 2,4-D, 2,4-DB, 2,4-DP, Desmedipham, Diallate, Dicamba, Diclofop (-methyl), Diclosulam, Diethatyl (-ethyl), Difenzoquat, Diflufenican, Diflufenzopyr, Dimefuron, Dimepiperate, Dimethachlor, Dimethametryn, Dimethenamid, Dimexyflam, Dinitramine, Diphenamid, Diquat, Di thiopyr, diuron, dymron, epropodan, EPTC, esprocarb, ethalfluralin, ethametsulf uron (-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanide, fenoxaprop- (-P-ethyl), fentrazamide, flamprop (-isopropyl), flamprop (-isopropyl-L), flamprop (- methyl), flazasulfuron, florasulam, fluazifop (-P-butyl), fluazolate, flucarbazone, Flufenacet, Flumetsulam, Flumiclorac (-pentyl), Flumioxazin, Flumipropyn, Flumet sulam, fluometuron, fluorochloridone, fluoroglycofen (-ethyl), flupoxam, fluprop acil, flurpyrsulfuron (-methyl, -sodium), flurenol (-butyl), fluridone, fluroxypyr (- meptyl), Flurprimidol, Flurtamone, Fluthiacet (-methyl), Fluthiamide, Fomesafen, Glufosinate (-ammonium), glyphosate (-isopropylammonium), halosafen, haloxyfop- (-ethoxyethyl), haloxyfop (-P-methyl), hexazinones, imazamethabenz (-methyl), Imazamethapyr, Imazamox, Imazapic, Imazapyr, Imazaquin, Imazethapyr, Imazo sulfuron, iodosulfuron (-methyl, -sodium), ioxynil, isopropalin, isoproturon, isouron,  Isoxaben, Isoxachlortole, Isoxaflutole, Isoxapyrifop, Lactofen, Lenacil, Linuron, MCPA, MCPP, Mefenacet, Mesotrione, Metamitron, Metazachlor, Methabenzthiaz uron, metobenzuron, metobromuron, (alpha-) metolachlor, metosulam, metoxuron, Metribuzin, Metsulfuron (-methyl), Molinate, Monolinuron, Naproanilide, Naprop amide, neburon, nicosulfliron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxa diazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendi methalin, pendralin, pentoxazone, phenmedipham, piperophos, pretilachlor, primi sulfuron (-methyl), prometryn, propachlor, propanil, propaquizafop, propisochlor, Propyzamides, prosulfocarb, prosulfuron, pyraflufen (-ethyl), pyrazolates, pyrazosulf uron (-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyriminobac (- methyl), pyrithiobac (-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop- (-P-ethyl), quizalofop (-P-tefuryl), rimsulfuron, sethoxydim, Simazine, Simetryn, Sulcotrione, sulfentrazone, sulfometuron (methyl), sulfosate, sulfosulirone, Tebutam, Tebuthiuron, Tepraloxydim, Terbuthylazine, Terbutryn, Thenylchlor, Thia fluamide, thiazopyr, thidiazimin, thifensulfuron (-methyl), thiobencarb, tiocarb azil, tralkoxydim, triallates, triasulfuron, tribenuron (-methyl), triclopyr, tri diphane, trifluralin and triflusulfuron.

A mixture with other known active ingredients, such as fungicides, Insecticides, acaricides, nematicides, bird repellants, plants nutrients and soil structure improvers are possible.

The active substances can be used as such, in the form of their formulations or in the form thereof application forms prepared by further dilution, such as ready-to-use Solutions, suspensions, emulsions, powders, pastes and granules are used become. The application is done in the usual way, e.g. B. by pouring, spraying, Spray, sprinkle.

The active compounds according to the invention can be used both before and after emergence of the plants are applied. They can also be planted in the soil before sowing be working.  

The amount of active ingredient used can vary over a wide range. she depends essentially 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 area, preferably between 5 g and 5 kg per ha.

The manufacture and use of the active compounds according to the invention start out the following examples.

Manufacturing examples example 1

A mixture of 1.1 g (20 mmol) sodium methylate, 6.2 g (20 mmol) 1- [1- (5- Chlor-4-methyl-thien-2-yl) propyl] biguanide, 2.4 g (20 mmol) of 2-fluoropropanoic acid methyl ester and 30 ml of methanol is ge for 18 hours at room temperature (about 20 ° C) stirs. Then with methylene chloride and water (Vol. Approx. 1: 1) to about that diluted five times in volume and shaken well. The organic phase will separated, dried with sodium sulfate and filtered. The solution becomes from the filtrate medium carefully distilled off under reduced pressure.

1.5 g (23% of theory) of 6- (1-fluoro-ethyl) -N ² - [1- (5-chloro-4-methyl-2-thienyl) propyl] -1.3.5 are obtained -triazine-2,4-diamine as an amorphous residue.
logP (at pH = 2.3): 2.47.

Analogously to Example 1 and in accordance with the general description of the production process according to the invention, it is also possible, for example, to prepare the compounds of the general formula (I) listed in Table 1 below.

Table 1

Examples of the compounds of the formula (I)

Examples of use

In some of the following application examples, the following known compound is used as a reference substance:

N ² - [1- (5-chloro-4-methyl-2-thienyl) propyl] -6-trifluoromethyl-1,3,5-triazine-2,4-diamine (known from JP-A-63222166)

Example A Pre-emergence test

Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the specified amount of solvent, specifies the added amount of emulsifier and dilute the concentrate with water to the ge wanted concentration.

Seeds of the test plants are sown in normal soil. After 24 hours the soil is sprayed with the active ingredient preparation so that the desired one Amount of active ingredient is applied per unit area. The drug concentration in the spray liquor is chosen so that in 1000 liters of water per hectare each desired amount of active ingredient is applied.

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% = no effect (like untreated control)
100% = total annihilation

In this test, for example, the compounds according to the preparation example show 1, 3 and 5 with good tolerance to crops, such as. B. Maize, considerably more effective against weeds than the known compound (A).  

Example B Post emergence test

Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the specified amount of solvent, specifies the added amount of emulsifier and dilute the concentrate with water to the ge wanted concentration.

With the active ingredient preparation, test plants are sprayed, which have a height of 5-15 cm have so that the desired amounts of active ingredient per unit area be applied. The concentration of the spray liquor is chosen so that in 1000 l water / ha the desired amounts of active ingredient are applied.

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% = no effect (like untreated control)
100% = total annihilation

In this test, for example, the compounds according to the preparation example show 1, 2, 3, 4 and 5 with good tolerance to crops, such as e.g. B. corn, strong action against weeds.

Claims (8)

1. Compounds of the general formula (I)
in which
R ^{1 represents} dihalomethyl, ethyl, haloethyl, dihaloethyl, n-propyl, halo-n-propyl, dihalo-n-propyl, i-propyl, halo-i-propyl, dihalo-i-propyl, halocyclopropyl, dihalo-cyclopropyl or trihalo-cyclopropyl,
R ^{2 represents} hydrogen or represents methyl, ethyl, n- or i-propyl which is optionally substituted by cyano, halogen, methoxy, ethoxy, n- or i-propoxy,
R ³ for hydrogen, for formyl or for methyl, ethyl, n- or i-propyl, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, optionally substituted by cyano, halogen, methoxy, ethoxy, n- or i-propoxy , Ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylamino carbonyl,
R ⁴ represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each optionally substituted by cyano, halogen, methoxy, ethoxy, n- or i-propoxy,
R ^{5 represents} chlorine or methyl and
R ^{6 represents} chlorine or methyl,
wherein the substituents on the carbon atom to which R ^{4 is} attached are essentially arranged either in the R configuration or in the S configuration, and also the respective racemates. 2. Compounds according to claim 1, characterized in that
R ¹ for difluoromethyl, dichloromethyl, dibromomethyl, chlorofluoromethyl, chlorobromomethyl, fluorobromomethyl, ethyl, fluoroethyl, chloroethyl, bromoethyl, difluoroethyl, dichloroethyl, dibromethyl, chlorofluoroethyl, bromofluoroethyl, n-propyl, fluoro-n-propyl, chloro-n-propyl, bromine -n propyl, difluoropropyl, dichloro-n-propyl, i-propyl, fluoro-i-propyl, chloro-i-propyl, bromo-i-propyl, difluoro-i-propyl, dichloro-i-propyl, fluorocyclopropyl, Chlorocyclopropyl, difluorocyclopropyl, dichlorocyclopropyl, trifluorocyclopropyl, trichlorocyclopropyl, chlorodifluorocyclopropyl or fluorodichlorocyclopropyl,
R ^{2 represents} hydrogen or methyl or ethyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,
R ^{3 represents} hydrogen, formyl or methyl, ethyl, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, Ethylaminocarbonyl, n- or i-propylaminocarbonyl,
R ⁴ represents methyl, ethyl, n- or i-propyl, each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,
R ^{5 represents} chlorine or methyl and
R ^{6 represents} chlorine or methyl. 3. Compounds according to claim 1, characterized in that
R ¹ for difluoromethyl, dichloromethyl, dibromomethyl, chlorofluoromethyl, ethyl, 1-fluoro-ethyl, 2-fluoro-ethyl, 1-chloro-ethyl, 2-chloro-ethyl, 1-bromo-ethyl, 2-bromo-ethyl, 1 , 1-difluoro-ethyl, 1,2-difluoro-ethyl, 2,2-difluoro-ethyl, 1,1-dichloro-ethyl, 1,2-dichloro-ethyl, 2,2-dichloro-ethyl, 1,2 -Dibromo-ethyl, 1-chloro-1-fluoroethyl, 1-chloro-2-fluoro-ethyl, 2-chloro-1-fluoro-ethyl, 2-chloro-2-fluoro-ethyl, 1-fluoro-n-propyl , 2-fluoro-n-propyl, 1-chloro-n-propyl, 2-chloro-n-propyl, 1-bromo-n-propyl, 2-bromo-n-propyl, 1-fluoro-i-propyl, 1 Chloro-i-propyl, difluorocyclopropyl or dichlorocyclopropyl,
R ^{2 represents} hydrogen, methyl or ethyl,
R ^{3 represents} hydrogen, formyl, methyl or ethyl, or acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, optionally substituted by fluorine, chlorine, methoxy or ethoxy , Ethylaminocarbonyl, n- or i-propylaminocarbonyl,
R ⁴ represents methyl, ethyl, n- or i-propyl, each optionally substituted by fluorine, chlorine, methoxy or ethoxy,
R ^{5 represents} chlorine or methyl and
R ^{6 represents} chlorine or methyl. 4. Compounds according to claim 1, characterized in that
R ¹ for difluoromethyl, dichloromethyl, chlorofluoromethyl, ethyl, 1-fluoroethyl, 1-chloroethyl, 1,1-difluoro-ethyl, 1,2-difluoro-ethyl, 1,1-dichloroethyl, 1,2-dichloro -ethyl, 1-chloro-1-fluoroethyl, 1-chloro-2-fluoro-ethyl, 2-chloro-1-fluoro-ethyl, 1-fluoro-n-propyl, 1-chloro-n-propyl, 1-fluorine isopropyl or 1-chloro-i-propyl,
R ^{2 represents} hydrogen,
R ^{3 represents} hydrogen, formyl or acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, each optionally substituted by fluorine, chlorine, methoxy or ethoxy,
R ⁴ represents methyl, ethyl, n- or i-propyl, each optionally substituted by fluorine or chlorine,
R ^{5 represents} chlorine and
R ^{6 represents} methyl. 5. A process for the preparation of the compounds according to any one of claims 1 to 4, characterized in that compounds of the general formula (II)
in which
R ² , R ³ , R ⁴ , R ⁵ and R ^{6 have} the meaning given in one of claims 1 to 4,
and / or acid adducts of compounds of the general formula (II)
with alkoxycarbonyl compounds of the general formula (III)
R ¹ -CO-OR '(III)
in which
R ^{1 has} the meaning given in one of claims 1 to 4 and
R 'represents alkyl,
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. A method for controlling unwanted vegetation, thereby characterized in that at least one connection according to one of the  Claims 1 to 4 on undesirable plants and / or their habitat can act. 7. Use of at least one compound according to one of the claims 1 to 4 for controlling unwanted plants. 8. Herbicidal agent, characterized by a content of a compound according to one of claims 1 to 4 and conventional extenders and / or surfactants.