WO2002010160A2 - Substituted heterocyclyl alkylamino-1,3,5-triazines - Google Patents

Abstract

The invention relates to substituted heterocyclyl alkylamino-1,3,5-triazines of general formula (I), in which R?1, R2, R3, R4 and R5¿ have the meanings cited in the description. The invention also relates to the use of the inventive compounds as selective herbicides, and to methods and intermediate products for the production thereof.

Description

Substituted heterocyclic ylamino-l, 3,5-triazines

The invention relates to new substituted heterocyclylalkylarnino-l, 3,5-triazme, processes for their preparation, intermediates for their production, ner processes for

Preparation of these intermediates and the use of the substituted heterocyclic alkylamino-l, 3,5-triazines as herbicides.

Some heterocyclylamino-l, 3,5-triazines from the BenztMazolylalkylamino-triazine series - specifically the compounds 2-amino-4- [l- (benzothiazol-2-yl) ethyl] -6- isopropyl-l, 3, 5-triazine and 2-aιrιώo-4- [l- (6-methyl-beιιzziazon-2-yl) ethyl] -6-isopropyl-l, 3,5-triazine - are already known (cf. DE- A-19604191). So far, however, these compounds have not gained any particular importance as crop protection agents.

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

in welcher

in which

R ¹ for optionally by amino, Νitro, cyano, carbamoyl, thiocarbamoyl, halogen, or by alkyl, alkoxy or alkoxycarbonyl, each optionally substituted by cyano, halogen or C 1 -C ₄ -alkoxy, each having up to 6 carbon atoms, or by in each case by optionally Νitro, cyano, halogen, C ₁ -C ₄ alkyl, dC / _t -haloalkyl, C ₁ -C ₄ alkoxy or

C 1 -C ₄ -Halogenalkoxy substituted phenyl or pyridyl substituted monocyclic heterocyclyl with 5 ring members, of which 1 to 3 carbon are atoms, are 1 to 4 nitrogen atoms and optionally one is an oxygen atom or a sulfur atom,

R ^{2 represents} alkyl with 1 to 6 carbon atoms optionally substituted by cyano, halogen or C.-C ₄ alkoxy or for optionally substituted by cyano,

Halogen or C.-C ₄ alkyl substituted cycloalkyl having 3 to 6 carbon atoms,

R ³ for hydrogen, for halogen, for alkyl with 1 to 6 carbon atoms substituted by cyano, halogen, hydroxy, C.-C ₄ -alkoxy or C.-C ₄ -alkylthio, for each optionally by cyano, halogen or C.- C ₄ - Alkoxy-substituted alkylcarbonyl, alkoxycarbonyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms in the alkyl groups, for each optionally substituted by halogen-substituted alkenyl or alkynyl each having 2 to 6 carbon atoms, or for optionally by Cyano, halogen or C.-C ₄ -alkyl-substituted cycloalkyl having 3 to 6 carbon atoms,

R ^{4 represents} hydrogen or alkyl which has 1 to 6 carbon atoms and is optionally substituted by cyano, halogen or C.-C ₄ alkoxy, and

R ^{5 represents} hydrogen, formyl or alkyl, alkylcarbonyl, alkoxycarbonyl or alkylaminocarbonyl, each of which has 1 to 6 carbon atoms in the alkyl groups, optionally substituted by cyano, halogen or C.-C ₄ alkoxy,

or the grouping N (R ⁴ R ⁵ ) also represents alkylaminoalkylamino or dialkylarnmoalkylideneamino, each having up to 6 carbon atoms in the alkyl groups or alkylidene groups,

found. Preferred substituents or ranges of the radicals present in the formulas listed above and below are described below:

R ¹ preferably represents optionally by amino, nitro, cyano, carbamoyl,

Thiocarbamoyl, halogen, or by alkyl, alkoxy or alkoxycarbonyl, each optionally substituted by cyano, halogen or CrC ₃ - alkoxy, each having up to 5 carbon atoms, or by in each case optionally by nitro, cyano, halogen, C 1 -C ₄ -alkyl, Cι- C haloalkyl, Cι-C ₄ alkoxy or Cι-C ₄ -haloalkoxy-substituted phenyl or pyridyl substituted monocyclic heterocyclyl having 5 ring members of which from 1 to 3 carbon atoms, 1 to 4 nitrogen atoms and optionally an oxygen atom or a sulfur atom ,

R ² preferably represents optionally cyano-, halogen or C.-C ₃ - alkoxy-substituted alkyl having 1 to 5 carbon atoms, or represents optionally cyano-, halogen or C.-C ₃ alkyl substituted cycloalkyl having 3 to 6 carbon atoms.

R ³ preferably represents hydrogen, halogen, alkyl substituted by cyano, halogen, hydroxy, C ₃ -C ₃ -alkoxy or C ₁ -C ₃ -alkylthio, with 1 to 5 carbon atoms, each optionally substituted by cyano, halogen or C ₁ -C ₃ alkoxy-substituted alkylcarbonyl, alkoxycarbonyl, alkoxy, alkylthio, alkylsulfmyl or alkylsulfonyl each having 1 to 5 carbon atoms in the alkyl groups, each optionally substituted by halogen

Alkenyl or alkynyl each having 2 to 5 carbon atoms, or for cycloalkyl having 3 to 6 carbon atoms optionally substituted by cyano, halogen or C 1 -C 4 alkyl. R ⁴ preferably represents hydrogen or alkyl having 1 to 5 carbon atoms which is optionally substituted by cyano, halogen or C.-C ₃ alkoxy.

R ⁵ preferably represents hydrogen, forrnyl or for alkyl, alkylcarbonyl, alkoxycarbonyl or alkylaminocarbonyl, each of which has 1 to 5 carbon atoms in the alkyl groups, which is optionally substituted by cyano, halogen or C.-C ₃ alkoxy.

The grouping N (R ⁴ R ⁵ ) preferably also represents alkylaminoalkylidene amino or dialkylaminoalkylidene amino each having up to 5 carbon atoms in the alkyl groups or alkylidene groups.

R ¹ particularly preferably represents in each case optionally substituted by amino, nitro, cyano, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine or by methyl, ethyl, n- or i-propyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy , n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, or by in each case optionally by nitro, cyano, fluorine, chlorine , Bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy substituted phenyl or Pyridyl substituted imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl or thiadiazolyl.

R ² particularly preferably represents methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, which is optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, or in each case cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl optionally substituted by cyano, fluorine, chlorine, bromine, methyl or ethyl. R particularly preferably represents hydrogen, fluorine, chlorine, bromine, in each case optionally substituted by cyano, fluorine, chlorine, bromine, hydroxy, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio Methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, for each acetyl, propionyl, n- or optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfmyl, n- or i-propylsulfinyl , Methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, for propenyl, butenyl, propynyl or butynyl, each optionally substituted by fluorine, chlorine or bromine, or for cyclopropyl optionally substituted by cyano, fluorine, chlorine, bromine, methyl or ethyl, Cyclobutyl, cyclopentyl or cyclohexyl.

R ⁴ particularly preferably represents hydrogen or methyl, ethyl, n- or i-propyl which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy.

R ⁵ particularly preferably stands for hydrogen, for formyl or for any substituted by cyano, fluorine, chlorine, methoxy or ethoxy

Methyl, ethyl, n- or i-propyl, acetyl, propionyl, n- or i-butyroyl,

Methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl.

The grouping N (R ⁴ R ⁵ ) particularly preferably also represents alkylaminoalkylidene amino or dialkylaminoalkylidene amino, each having up to 3 carbon atoms in the alkyl groups or alkylidene groups.

R ¹ very particularly preferably represents optionally substituted by nitro, cyano, fluorine, chlorine, bromine, or by methyl, ethyl, n- or i-propyl optionally substituted by fluorine, chlorine, methoxy or ethoxy, or by in each case optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy or trifluoromethoxy substituted phenyl or pyridyl.

R very particularly preferably represents in each case optionally by fluorine or

Chlorine substituted methyl, ethyl, n- or i-propyl, or for cyclopropyl optionally substituted by fluorine, chlorine or methyl.

R very particularly preferably represents methyl, ethyl, n- or i-propyl optionally substituted by fluorine or chlorine, or cyclopropyl optionally substituted by fluorine, chlorine or methyl.

R ⁴ very particularly preferably represents hydrogen, methyl or ethyl.

R very particularly preferably represents hydrogen, formyl, methyl or

Ethyl, or for acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl optionally substituted by fluorine, chlorine, methoxy or ethoxy.

The grouping N (R ⁴ R ⁵ ) very particularly preferably also represents dimethylaminomethyleneamino.

R most preferably represents methyl, ethyl, n- or i-propyl, each optionally substituted by fluorine or chlorine.

R ⁴ most preferably represents hydrogen.

R ⁵ most preferably stands for hydrogen, for formyl, or for methoxycarbonyl or ethoxycarbonyl optionally substituted by fluorine, chlorine, methoxy or ethoxy. The general or preferred residues 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 residual definitions can be combined with one another, that is, also between the specified preferred ranges.

According to the invention, preference is given to those compounds of the formula (I) in which there is a combination of the meanings given above as preferred (“preferably”).

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

Those compounds of the formula (I) which have a combination of the meanings listed above as being very particularly preferred are very particularly preferred according to the invention.

Most 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 most preferred.

Saturated or unsaturated hydrocarbon radicals, such as alkyl or alkenyl, are in each case straight-chain or branched as far as possible, even in conjunction with heteroatoms, such as in alkoxy.

Optionally substituted radicals can be mono- or polysubstituted, whereby in the case of multiple substitution the substituents can be the same or different. The compounds of the general formula (I) according to the invention contain at least one asymmetrically substituted carbon atom and can therefore be present in various enantiomeric (R- and S-configured forms) or diasteromeric forms. The invention relates both to the various possible individual enantiomeric or stereoisomeric forms of the compounds of the general

Formula (I) as well as the mixtures of these isomeric compounds.

The new substituted heterocyclylal] cylamino-1,3,5-triazines of the general formula (I) have interesting biological properties. They are particularly characterized by their strong herbicidal activity.

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

in welcher

in which

l, R ^, R4 and R ^ 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 ³ -CO-OR '(III) in which

R ^{3 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, l- (1,3-thiazol-4-yl-ethyl) biguanide and methyl trifluoroacetate 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, R ^, R4 and

R5 preferably or in particular those meanings which have already been given above in connection with the description of the compounds of the general formula (I) according to the invention preferably or as particularly preferred for Rl, R ^, R4 and R5.

Suitable acid adducts of compounds of the 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. The new biguanides of the general formula (II) are obtained if amino compounds of the general formula (IN)

in welcher

in which

1

R and R have the meaning given above,

and / or acid adducts of compounds of the general formula (IV), such as e.g. the hydrochloride -

with cyanoguanidine ("dicyandiamide") of the formula (V)

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).

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) ,

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 anriino compounds of the general formula (IN) required as precursors are known and / or can be prepared by known processes (cf. US-A-4829053, US-A-5173496, US-A-5998470, production 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 Nerbindungen of the general formula (I). In the general formula (III), R preferably or in particular has the meaning which has already been mentioned above in connection with the description of the inventive compounds of the general formula (I), 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 synthetic chemicals.

The process according to the invention for producing the compounds of the general formula (I) is preferably carried out using a reaction auxiliary. The usual inorganic or organic bases or acid acceptors are generally suitable as reaction aids. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkanolates, such as sodium, potassium or calcium acetate, lithium, sodium, potassium or Calcium amide, sodium, potassium or calcium carbonate, sodium, potassium or calcium hydrogen carbonate, lithium, sodium, potassium or calcium hydride, lithium, sodium, potassium or calcium hydroxide, Sodium or potassium methoxide, ethanolate, n or i propanolate, n, i, s or t butanolate; also basic organic nitrogen compounds, such as trimethylamine, trifethylamine, tripropylamine, tributylamine, ethyl diisopropylamine, N, N-dimethylcyclohexylamine, dicyclohexylamine, ethyl dicyclohexylamine, 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-en (DBU). The process according to the invention for the preparation of the compounds of the general formula (I) is preferably carried out using a diluent. Inert organic solvents are particularly suitable as diluents for carrying out the process according to the invention. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers such as diethyl ether, diisopropyl ether, dioxane, tefrahydrofuran 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-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide.

The reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 120 ° C.

The process according to the invention is generally carried out under normal pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressure - generally between 0.1 bar and 10 bar.

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. The up work is carried out according to customary methods (cf. the manufacturing examples).

The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers.

Weeds in the broadest sense are all plants that grow in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can e.g. can be used in the following plants:

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, Rorippex, Rotal Salsola, Senecio, Sesbania, 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.

Monocotyledon 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, Seeale, Sorghum, Triticale, Triticum, Zea.

However, the use of the active compounds according to the invention is by no means limited to these

Limited genera, but extends in the same way to other plants.

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

Because of and places 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 areas and for selective weed control in annual crops.

The compounds of formula (I) according to the invention show strong herbicidal activity and a broad spectrum of activity when used on the soil and on above-ground parts of plants. To a certain extent, they are also suitable for selective use

Control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops, both pre- and post-emergence.

In certain concentrations or application rates, the active compounds according to the invention can also be used to control animal pests and fungal or bacterial plant diseases. If appropriate, they can also be used as intermediates or precursors for the synthesis of further active compounds.

According to the invention, all plants and parts of plants can be treated. Under

Plants are understood to mean all plants and plant populations, such as wanted and unwanted wild plants or crops (including naturally occurring crops). 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 shoots, leaves, flowers and roots, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.

The treatment of the plants and plant parts according to the invention with the active substances takes place directly or by acting on their environment, habitat or

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

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, that is liquid solvents and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example 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.

Possible solid carriers are: e.g. Ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite,

Marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foaming agents are possible: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol

Ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersants are: e.g. Lignin sulfite leaching and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils. Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin,. Azo and metal 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, as such or in their formulations, can also be mixed with known herbicides and / or with substances which

Improving crop compatibility ("safeners") can be used for weed control, ready-to-use formulations or tank mixes being possible. Mixtures with weed control compositions which contain one or more known herbicides and a safener are also possible.

Known herbicides are suitable for the mixtures, for example

Acetochlor, Acifluorfen (-sodium), Aclonifen, Alachlor, Alloxydim (-sodium), Ametryne, Amicarbazone, Amidochlor, Arnidosulfuron, Anilofos, Asulam, Atrazine, Azafenidin, Azimsulfuron, Beflubutamid, Benazolin (-ethyl), Benulfureson -methyl), bentazone, benzfendizone, benzobicyclone, benzofenap, benzoylprop (-ethyl), bialaphos, bifenox, bispyribac (-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butafenacil (-allyl), butroxydim, butylate, cafenimole, cafenimole Carbetamides, Carfentrazone (-ethyl), Chlomefhoxyfen, Chloramben, Chloridazon, Chlorimuron (-ethyl), Chlornitrofen, Chlorsulfuron, Chlortoluron, Cinidone (-ethyl), Cinmethylin, Cinosulfuron, Clefoxydim, Clethodim, Clodinafop (-proomodonafop) Clomeprop, Clopyralid, Clopyrasulfluron (-methyl), Clor- ansulam (-methyl), Cumyluron, Cyanazines, Cybutryne, Cycloate, Cyclosulfamuron, Cycloxydim, Cyhalofop (-butyl), 2,4-D, 2,4-DB, Desmedipham, Dialates, dicamba, dichloroprop (-P), diclofop (-methyl), diclosul am, diethatyl (-ethyl), difenzoquate,

Diflufenican, Diflufenzopyr, Dimefuron, Dimepiperate, Dimethachlor, Dimetha- metryn, Dimethenamid, Dimexyflam, Dinitramine, Diphenamid, Diquat, Dithiopyr, Diuron, Dymron, Epropodan, EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron (-methyl), Ethofumesate, Ethoxyfen, Ethoxysulfuron, EthobenzanidPhenox, Fenox Flamprop (-isopropyl, -isopropyl-L, -methyl), flazasulfuron, florasulam, fluazifop (-P-butyl), fluazolate, flucarbazone (-sodium), flufenacet,

Flumetsulam, flumiclorac (-pentyl), flnmioxazin, flumipropyn, fluometuron, fluorochloridone, fluoroglycofen (-ethyl), flupoxam, flupropacil, flurpyrsulfuron (-methyl, -sodium), flurenol (-butyl), fluridyl-fluridyl-fluridyl-fluridyl-fluridyl-fluridyl ), Flurprimidol, Flurtamone, Fluthiacet (-methyl), Fluthiamide, Fomesafen, Foramsulfuron, Glufosinate (-ammonium), Glyphosate (-isopropylammonium),

Halosafen, Haloxyfop (-ethoxyethyl, -P-methyl), Hexazinone, Imazamethabenz (-methyl), Imazamethapyr, Imazamox, Imazapic, Imazapyr, Imazaquin, Imazethapyr, hnazosulfuron, Iodosulfuron (-methyl, -sodium), Ialinolophenil Isouron, Isoxaben, Isoxachlortole, Isoxaflutole, Isoxapyrifop, Lactofen, Lenacil, Linuron, MCPA, Mecoprop, Mefenacet, Mesotrione, Metamitron, Metazachlor, Metha benzthiazuron, Metobenzuron, Metobromuron, (alpha-) Metolacholamiboramamibor metsulfuron (-methyl), molinate, monolinuron, Napro- anilides, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, Oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, Pendralin, Pentoxazone, phenmedipham, picolinafen,

Piperophos, Pretilachlor, Primisulfuron (-methyl), Profluazol, Prometryn, Propachlor, Propanil, Propaquizafop, Propisochlor, Propoxycarbazone (-sodium), Propyzamide, Prosulfocarb, Prosulfüron, Pyraflufen (-ethyl), Pyrazogyl, Pyrazolonate, Pyrazolonate Pyrazoxyfen, Pyribenzoxim, Pyributicarb, Pyridate, Pyridatol, Pyriftalid, Pyriminobac (-methyl), Pyrithiobac (-sodium), Quinchlorac, Quinmerac, Quinoclamine, Quizalofop (-P-ethyl, -P-tefuryl), Rimsulfuron, Simine , Simetryn, Sulcotrione, Sulfentrazone, Sulfometuron (-methyl), Sulfosate, Sulfosulfuron, Tebutam, Tebuthiuron, Tepraloxydim, Terbuthylazine, Terbutryn, Thenylchlor, Thiafluamide, Thiazopyr, Thidiazimin, Thifensulfuron- carboxeno , Triallate, Triasulfuron, Tribenuron (-methyl), Triclopyr, Tridiphane, Trifluralin, Trifloxysulfuron, Triflusulfi ron (-methyl), Tritosulfuron. 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 preparation and use of the active compounds according to the invention can be seen from the examples below.

Preparation Examples:

example 1

A mixture of 9.8 g (30 mmol) l - [(2-phenyl-l, 3-thiazol-4-yl) ethyl] biguanide hydrochloride (racemic), 4.0 g (33 mmol) 2- Fluor-isobutyric acid methyl ester and 60 ml of methanol are stirred for 10 minutes at room temperature (approx. 20 ° C.), then mixed with 33 ml of a 1 molar solution of sodium methylate in methanol and stirred for 15 hours at room temperature. Then it is diluted with 200 ml of water, the crystalline product is isolated by suction and unicrystallized from methanol water (vol. 1: 1).

6.6 g (62% of theory) of 6- (l-fluoro-l-methyl-ethyl) -N ² - [l- (2-ρhenyl-l, 3-thiazol-4-yl) ethyl] are obtained. - 1,3,5-2,4-diamine (racemate).

LogP (at pH = 2.3): 2.09.

Example 2

A mixture of 9.0 g (34 mmol) l - [(2-methyl-l, 3-thiazol-4-yl) ethyl] biguanide hydrochloride (racemic), 4.5 g (37.5 mmol) 2-fluoro-isobutyric acid methyl ester and

60 ml of methanol is stirred for 10 minutes at room temperature (approx. 20 ° C.), then mixed with 35 ml of a 1 molar solution of sodium methylate in methanol and stirred for 15 hours at room temperature. The solvent is then distilled off under reduced pressure, the residue is taken up in dichloromethane, washed with water, dried with sodium sulfate and filtered. The solvent is carefully distilled off from the filate under reduced pressure.

8.9 g (93% of theory) of 6- (l-fluoro-ethyl) -N ² - [l- (2-methyl-l, 3-thiazol-4-yl) -ethyl] -l, 3 are obtained , 5-2,4-diamine (racemate) as an amorphous product. LogP (pH = 2.3): 0.67.

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 Nerbindungen of the general formula (I) listed in Table 1 below.

Table 1: Examples of the compounds of the formula (I)

The logP values given in Table 1 were determined in accordance with EEC Directive 79/831 Annex N.A8 by HPLC (High Performance Liquid Chromatography) on a phase reversal 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) 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 ).

The calibration was carried out with unbranched alkan-2-ones (with 3 to 16 carbon atoms) whose logP values are known (determination of the logP values using the

Retention times by linear interpolation between two consecutive alkanones).

The lambda max values were determined using the UN spectra from 200 nm to 400 nm in the maxima of the chromatographic signals. Starting materials of formula (II):

Example (ü-1)

A solution of 20.5 g (0.11 mol) of 1- (2-phenyl-1,3-thiazol-4-yl) ethylamine (racemic) in 200 ml of toluene and 30 ml of decane is 30% with 12 g added aqueous hydrochloric acid and heated to boiling, the water being removed using a water separator. 8.4 g (0.10 mmol) of cyanoguanidine (“dicyandimide”) are then added and the reaction mixture is stirred at 140 ° C. for 2 hours.

After cooling, the mixture is stirred with acetone and the crystalline product is isolated by suction.

23 g (66% of theory) of l - [(2-phenyl-1,3-thiazol-4-yl) ethyl] biguanide (racemate) are obtained, which melts above 240 ° C.

Example (fl-2)

A solution of 5.0 g (35 mmol) of 1- (2-methyl-1,3-thiazol-5-yl) -ethylamine (racemic) in 150 ml of toluene and 30 ml of decane is mixed with 4.5 g of 30% added aqueous hydrochloric acid and heated to boiling, the water being removed using a water separator. Then 3.0 g (35 mmol) of cyanoguanidine (“dicyandimide”) are added and the reaction mixture is stirred for 2 hours at 150 ° C. After cooling to room temperature, the solvent is decanted off.

The l - [(2-memyl-l, 3-tMazol-5-yl) -e yl] -biguatid (racemate) remaining as a solid is used for the next stage (see Example 2) without further purification.

Analogously to Examples (II-1) and (II-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 (II) listed in Table 2 below.

Table 2: Examples of the compounds of the formula (II)

These are the hydrochlorides. The melting point is above 240 ° C in each case.

Input substances of the formula (TV):

Example (IV- 1)

step 1

27 g of thiobenzamide are added in portions to a solution of 36 g of l-bromo-diacetyl-3-monoxime in 200 ml of methanol and the mixture is added for 2 hours

Reflux heated. After cooling to room temperature, the mixture is diluted with 600 ml of water and made alkaline with saturated aqueous ammonia solution. The crystalline product is isolated by suction and dried.

29 g of 1- (2-phenyl-1,3-thiazol-4-yl) -ethanone oxime are obtained from the melting point

178 ° C.

This compound is already known from the literature (cf. US-A-4132798) and is also commercially available.

Level 2

25 g Lit umalunriniumhydrid (LiAlEL_t) werden in 350 ml Tefrahydrofuran bei 20°C bis 40°C vorgelegt. Bei 40°C bis 50°C werden innerhalb von 30 Minuten 65,5 g 1- (2-Phenyl-l,3-thiazol-4-yl)-ethanonoxim dazu gegeben und die Mischung wird dann 2 Stunden unter Rückfluss erhitzt. Nach Abkühlen auf Raumtemperatur werden bei 20°C bis 30°C 300 ml Wasser innerhalb einer Stunde dazu gegeben. Dann werden

25 g Lit umalunriniumhydrid (LiAlEL _t ) are placed in 350 ml tefrahydrofuran at 20 ° C to 40 ° C. At 40 ° C to 50 ° C, 65.5 g of 1- (2-phenyl-l, 3-thiazol-4-yl) ethanone oxime are added over 30 minutes and the mixture is then heated under reflux for 2 hours. After cooling to room temperature, 300 ml of water are added at 20 ° C to 30 ° C within one hour. Then be

700 ml of dichloromethane were added. After filtration, the organic phase is separated off, dried with sodium sulfate and filtered. The filtrate is concentrated and the residue is distilled under reduced pressure.

40 g of l- (2-phenyl-l, 3-thiazol-4-yl) ethylamine (racemate) are obtained from the boiling point

120 ° C (at 2 mbar).

The compound 1- (2-phenyl-1,3-thiazol-4-yl) ethylamine is not yet known from the literature; as a new substance it is also the subject of the present avoidance.

Example (JN-2)

step 1

35 g 2-Brom-3-oxo-butanal werden zu einer Lösung von 15 g Thioacetamid in 200 ml Aceton gegeben und die Mischung wird 15 Stunden bei Raumtemperatur (ca. 20°C) gerührt. Das kristallin angefallene Produkt wird durch Absaugen isoliert.

35 g of 2-bromo-3-oxo-butanal are added to a solution of 15 g of thioacetamide in 200 ml of acetone and the mixture is stirred for 15 hours at room temperature (approx. 20 ° C.). The crystalline product is isolated by suction.

27 g of l- (2-methyl-thiazol-5-yl) -ethanone (logP = 2.07 at ρH = 2.3) are obtained, which is hygroscopic and is rapidly implemented.

Level 2

A solution of 20 g of sodium hydroxide in 80 ml of water is added to a mixture of 44 g of l- (2-methyl-thiazol-5-yl) ethanone, 20 g of hydroxylamine hydrochloride and 150 ml of methanol at 20 ° C. to 40 ° C. given dropwise. The reaction mixture is then stirred for 15 hours at room temperature (approx. 20 ° C.) and then concentrated under reduced pressure. The residue is dissolved in acetone and filtered.

The solvent is carefully distilled off from the filtrate under reduced pressure.

L- (2-Methylthiazol-5-yl) ethanone oxime is obtained as an amorphous residue.

The compound 1- (2-methyl-thiazol-5-yl) -ethanone oxime is not yet known from the literature; as a new substance, it is also the subject of the present application. level 3

8 g of l- (2-methyl-thiazol-5-yl) -ethanone oxime are concentrated in a mixture of 50 ml. Hydrochloric acid and 30 ml of water and stirred at 20 ° C to 50 ° C with 15 g of zinc

Granules added. The reaction mixture is stirred for 6 hours at 60 ° C., then made alkaline with 4N sodium hydroxide solution and finally shaken with methylene chloride. The organic phase is separated off, dried with sodium sulfate and filtered. The filtrate is concentrated and the residue is distilled under reduced pressure.

2.5 g of l- (2-methyl-l, 3-thiazol-5-yl) ethylamine (racemate) with a boiling point of 70 ° C. (at 2 mbar) are obtained.

The compound 1- (2-methyl-1,3-thiazol-5-yl) -ethylamine is not yet out of the

Literature known; as a new substance, it is also the subject of the present application.

Application examples:

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, 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 concentration of active ingredient in the spray liquor is chosen so that the desired amount of active ingredient is applied in 1000 liters of water per hectare.

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 destruction

In this test, for example, the compounds according to Preparation Examples 1, 4, 6, 11 and 19, with good tolerance to crop plants, such as, for example, maize and soybeans, show a strong action against weeds. Table AI: Pre-emergence test / greenhouse

Table A2: Pre-emergence test / greenhouse

Table A3: Pre-emergence test / greenhouse

Table A4: Pre-emergence test / greenhouse

Beispiel B

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, 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

Concentration.

Test plants which have a height of 5-15 cm are sprayed with the active substance preparation in such a way that the desired amounts of active substance are applied per unit area. The concentration of the spray liquor is chosen so that in

1000 1 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 destruction

In this test, for example, the compounds according to Preparation Examples 1, 2, 3, 8, 12, 14, 15 and 17, with good tolerance to crop plants such as, for example, maize and wheat, show a strong action against weeds. Table B1: Post emergence test / greenhouse

Table B2: Post emergence test / greenhouse

Table B3: Post emergence test / greenhouse

Table B4: Post emergence test / greenhouse

Claims

Patentansprttche 1. Compounds of the general formula (I)

in which R for optionally by amino, nitro, cyano, carbamoyl, thiocarbamoyl, halogen, or by alkyl, alkoxy or alkoxycarbonyl, each optionally substituted by cyano, halogen or C 1 -C ₄ -alkoxy, each having up to 6 carbon atoms, or by in each case optionally by nitro, cyano, halo, Cι-C -alkyl, C ₄ haloalkyl, Cι-C ₄ alkoxy or Cι-C ₄ -haloalkoxy-substituted phenyl or pyridyl substituted monocyclic hetero-cyclyl having 5 ring members of which from 1 to 3 are carbon atoms, 1 to 4 nitrogen atoms and optionally one is an oxygen atom or a sulfur atom, R represents optionally cyano-, halogen or C.-C ₄ - alkoxy-substituted alkyl having 1 to 6 carbon atoms or represents optionally cyano-, halogen or C.-C ₄ -alkyl-substituted cycloalkyl having 3 to 6 carbon atoms, R for hydrogen, for halogen, for through cyano, halogen, hydroxy, C.- C ₄ -alkoxy or C.-C ^ alkylthio substituted alkyl having 1 to 6 carbon atoms, for each optionally substituted by cyano, halogen or C.-C ₄ -alkoxy substituted alkylcarbonyl, alkoxycarbonyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each with 1 to 6 carbon atoms in the alkyl groups, each represents alkenyl or alkynyl which is optionally substituted by halogen, each having 2 to 6 carbon atoms, or represents cycloalkyl having 3 to 6 carbon atoms which is optionally substituted by cyano, halogen or C.-C ₄ -alkyl, R ^{4 represents} hydrogen or alkyl having 1 to 6 carbon atoms which is optionally substituted by cyano, halogen or C.-C ₄ alkoxy, and R ^{5 represents} hydrogen, formyl or alkyl, alkylcarbonyl, alkoxycarbonyl or alkylaminocarbonyl, each of which has 1 to 6 carbon atoms in the alkyl groups, optionally substituted by cyano, halogen or C.-C ₄ -alkoxy, or the grouping N (R ⁴ R ⁵ ) is also alkylaminoalkylidene amino or dialkylaminoalkylidene amino, each having up to 6 carbon atoms in the alkyl groups or alkylidene groups. Compounds according to claim 1, characterized in that R ¹ for optionally by amino, nitro, cyano, carbamoyl, thiocarbamoyl, halogen, or by alkyl, alkoxy or alkoxycarbonyl, each optionally substituted by cyano, halogen or C ₁ -C ₃ -alkoxy, each having up to 5 carbon atoms, or by in each case optionally substituted by nitro, cyano, halo, Cι-C ₄ -alkyl, C ₄ haloalkyl, -C ₄ alkoxy or Cι-C ₄ -haloalkoxy-substituted phenyl or pyridyl substituted monocyclic hetero-cyclyl having 5 ring members of which from 1 to 3 are carbon atoms, 1 to 4 nitrogen atoms and optionally one is an oxygen atom or a sulfur atom, R represents optionally cyano-, halogen or C.-C ₃ - substituted alkoxy alkyl having 1 to 5 carbon atoms, or represents optionally cyano-, halogen or C.-C ₃ alkyl substituted cyclo alkyl is of 3 to 6 carbon atoms, R for hydrogen, for halogen, for alkyl with 1 to 5 carbon atoms substituted by cyano, halogen, hydroxy, C.- C ₃ -alkoxy or C.-C ₃ -alkylthio, for each optionally by cyano, halogen or C.-C ₃ -alkoxy substituted alkylcarbonyl, alkoxycarbonyl, Alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 5 carbon atoms in the alkyl groups, represents in each case optionally halogen-substituted alkenyl or alkinyl each having 2 to 5 carbon atoms, or represents optionally cyano-, halogen or C.-C _j-alkyl cycloalkyl has 3 to 6 carbon atoms, R ^{4 represents} hydrogen or alkyl having 1 to 5 carbon atoms which is optionally substituted by cyano, halogen or C.-C ₃ alkoxy, and R ^{5 represents} hydrogen, formyl or alkyl, alkylcarbonyl, alkoxycarbonyl or alkylaminocarbonyl, each of which has from 1 to 5 carbon atoms in the alkyl groups, optionally substituted by cyano, halogen or C.-C ₃ alkoxy, or the grouping N (RR ⁵ ) also stands for alkylaminoalkylidene amino or dialkylammoalkylidene amino each having up to 5 carbon atoms in the alkyl groups or alkylidene groups. 3. Compounds according to claim 1, characterized in that R ^{1 is} in each case optionally substituted by amino, nitro, cyano, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, or by methyl, ethyl, n- or i-propyl, n- which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy , i-, s- or t-butyl, methoxy, Ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, or by in each case optionally by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i -, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy substituted phenyl or pyridyl substituted imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl or thiadiazolyl R for each methyl, ethyl, n- or i- substituted by cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy Propyl, n-, i- or s-butyl, or represents cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, which are each optionally substituted by cyano, fluorine, chlorine, bromine, methyl or ethyl, R for hydrogen, for fluorine, chlorine, bromine, for methyl, ethyl substituted in each case optionally by cyano, fluorine, chlorine, bromine, hydroxy, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio , n- or i-propyl, n-, i- or s-butyl, for in each case optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, acetyl, propionyl, n- or i-butyroyl, Methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, for propenyl optionally substituted by fluorine, chlorine or bromine, Butenyl, propynyl or butynyl, or for optionally by cyano, Fluorine, chlorine, bromine, methyl or ethyl substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, R ^{4 represents} hydrogen or methyl, ethyl, n- or i- which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy Propyl stands, and R ⁵ for hydrogen, for formyl or for each optionally by Cyano, fluorine, chlorine, methoxy or ethoxy substituted methyl, ethyl, n- or i-propyl, acetyl, propionyl, n- or i-butyroyl, Methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl, or the grouping N (R ⁴ R ⁵ ) also stands for alkylaminoalkylidene amino or dialkylanriinoalkylidene amino each having up to 3 carbon atoms in the alkyl groups or alkylidene groups. Compounds according to claim 1, characterized in that R ^{1 represents} methyl, ethyl, n- or i-propyl optionally substituted by nitro, cyano, fluorine, chlorine, bromine, or by methyl, ethyl, n- or i-propyl, optionally substituted by fluorine, chlorine, methoxy or ethoxy, or by fluorine, chlorine, bromine, if appropriate, Methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy or trifluoromethoxy substituted phenyl or pyridyl substituted thiazolyl, R represents methyl, ethyl, n- or i-propyl which is optionally substituted by fluorine or chlorine, or represents cyclopropyl which is optionally substituted by fluorine, chlorine or methyl, R ^{3 represents} in each case methyl, ethyl, n- or i-propyl optionally substituted by fluorine or chlorine, or cyclopropyl optionally substituted by fluorine, chlorine or methyl, R ^{4 represents} hydrogen, methyl or ethyl, and R ^{5 represents} hydrogen, formyl, methyl or ethyl, or acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl which are optionally substituted by fluorine, chlorine, methoxy or ethoxy, or the grouping N (R _> 4 _π R5) also represents dimethylammomethyleneamino. 5. A method for producing connections according to claim 1, characterized in that Biguanides of the general formula (II)

in which Rl, R ^, R4 and Tlß have the meaning given in claim 1, and / or acid adducts of compounds of the general formula (II) with alkoxycarbonyl compounds of the general formula (III) R ³ -CO-OR '(πi) in which R ^{3 has} the meaning given in claim 1 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, characterized in that at least one compound according to one of claims 1 to 4 is allowed to act on undesired plants and / or their habitat. 7. Use of at least one compound according to one of 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 surface-active agents. Compounds of the general formula (II)

in which Rl, R2, R4 and R ^ have the meaning given in claim 1, - And / or acid adducts of compounds of the general formula (II) -. 10. The compounds 1- (2-phenyl-1,3-thiazol-4-yl) -ethylamine, 1- (2-methyl-thiazol-5-yl) -ethanone oxime, 1- (2-methyl-1,3-yl -thiazol-5-yl) ethylamine.