WO2000047579A1

WO2000047579A1 - Substituted benzthiazolylalkylamino-1,3,5-triazines as herbicides

Info

Publication number: WO2000047579A1
Application number: PCT/EP2000/000785
Authority: WO
Inventors: Hans-Jochem Riebel; Mark Wilhelm Drewes; Kristian Kather; Dieter Feucht; Rolf Kirsten; Rolf Pontzen; Stefan Lehr; Ingo Wetcholowsky; Katharina Voigt
Original assignee: Bayer Aktiengesellschaft
Priority date: 1999-02-11
Filing date: 2000-02-01
Publication date: 2000-08-17
Also published as: DE19905609A1; AU2546200A

Abstract

The invention relates to novel substituted benzthiazolylalkylamino-1,3,5-triazines of general formula (I), wherein n, R?1, R2, R3, R4 and R5¿ have the meanings given in the description, to methods and intermediate products for producing them, including the method for producing said intermediate products and to the use of the inventive benzthiazolylalkylamino-1,3,5-triazines as herbicides.

Description

SUBSTITUTED BENZTHIAZ0LYLAL YLAMIN0-1.3.5-TRIAZINE AS HERBICIDES

The invention relates to new substituted benzthiazolylalkylamino-l, 3,5-triazines, processes for their preparation, intermediates for their preparation, processes for the preparation of these intermediates and the use of the benzothiazolylalkylamino-l, 3,5-triazines as herbicides.

Some benzothiazolylalkylaminotriazines - specifically the compounds 2-amino- 4- [l- (benzthiazol-2-yl) ethylamino] -6-isopropyl-l, 3,5-triazine and 2-amino-4- [l- (6 - methyl-benzthiazol-2-yl) -ethylamino] -6-isopropyl-l, 3,5-triazine - are already known

(see DE-A-19604191). However, these compounds have so far had no particular importance as crop protection agents.

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

in which

n stands for the numbers 0, 1, 2, 3 or 4,

R stands for nitro, cyano, carbamoyl, thiocarbamoyl, halogen or for alkyl or alkoxy each having 1 to 6 carbon atoms each optionally substituted by cyano, halogen or -CC alkoxy,

R is optionally substituted by cyano, halogen or C _j -C ₄ alkoxy

Alkyl with 1 to 6 carbon atoms or for optionally by cyano, Halogen or C 1 -C ₄ -alkyl-substituted cycloalkyl having 3 to 6 carbon atoms,

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

Is alkoxy-substituted alkyl having 1 to 6 carbon atoms, and - R represents hydrogen or represents optionally cyano-, halogen or C _j -C ₄

R ⁵ represents hydrogen, represents formyl or represents in each case optionally cyano-, halogen or C _j -C ₄ - in the alkyl groups substituted alkoxy alkyl, alkylcarbonyl, alkoxycarbonyl or alkylaminocarbonyl having in each case 1 to 6 carbon atoms,

or the grouping N (R ⁴ R ⁵ ) also represents alkylaminoalkylidene amino or dialkylaminoalkylidene amino 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:

n preferably represents the numbers 0, 1, 2 or 3. R preferably stands for nitro, cyano, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, iodine, or for alkyl or alkoxy, each substituted by cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i-propoxy, each having 1 up to 5 carbon atoms.

R preferably represents alkyl having 1 to 5 carbon atoms which is optionally substituted by cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i-propoxy or cycloalkyl which is optionally substituted by cyano, fluorine, chlorine, bromine, methyl or ethyl up to 6 carbon atoms.

R preferably represents hydrogen, fluorine, chlorine, bromine, cyano, fluorine, chlorine, bromine, hydroxy, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio substituted alkyl with 1 to 5 carbon atoms, each optionally with cyano, fluorine, chlorine, methoxy,

Ethoxy, n- or i-propoxy-substituted alkylcarbonyl, alkoxycarbonyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 5 carbon atoms in the alkyl groups, for alkenyl or alkynyl each optionally substituted by fluorine, chlorine or bromine, each having 3 to 5 carbon atoms, or for optionally by cyano, fluorine, chlorine,

Bromine, methyl or ethyl substituted cycloalkyl with 3 to 6 carbon atoms.

R preferably represents hydrogen or alkyl having 1 to 5 carbon atoms which is optionally substituted by cyano, fluorine, chlorine, bromine, methoxy or ethoxy.

R preferably represents hydrogen, formyl or alkyl, alkylcarbonyl, alkoxycarbonyl or alkylaminocarbonyl, each of which is optionally substituted by cyano, fluorine, chlorine, bromine, methoxy or ethoxy, each having 1 to 5

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

n particularly preferably represents the numbers 0, 1 or 2.

R ¹ particularly preferably represents nitro, cyano, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, or methyl, ethyl, n- or i-propyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,

Methoxy, ethoxy, n- or i-propoxy.

R particularly preferably represents in each case optionally by cyano, fluorine,

Chlorine, methoxy or ethoxy substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, or for each optionally by cyano, fluorine, chlorine,

Bromine, methyl or ethyl substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

R ³ particularly preferably represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, each substituted by cyano, fluorine, chlorine, bromine, hydroxyl, methoxy, ethoxy, methylthio or ethylthio, i- or s-butyl, for in each case optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propyl thio, methylsulfmyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, for propenyl, butenyl, propynyl or butynyl optionally substituted by fluorine, chlorine or bromine, or for cyclopropyl, cyclobutyl, each optionally substituted by cyano, fluorine, chlorine, bromine, methyl or ethyl, Cyclopentyl or cyclohexyl. R particularly preferably represents hydrogen or methyl, ethyl, n- or i-propyl which is optionally substituted by cyano, fluorine, chlorine, bromine, methoxy or ethoxy.

R particularly preferably represents hydrogen, formyl or methyl, ethyl, n- or i-propyl, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, which are each optionally substituted by cyano, fluorine, chlorine, bromine, methoxy or ethoxy, Ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl.

The grouping N (R ⁴ R ⁵ ) particularly preferably also stands for methylamino-methylenamino (N = CH-NHCH ₃ ), ethylaminomethyleneamino (N = CH-NHC ₂ H ₅ ), n- or i-propylaminomethyleneamino (N = CH-NHC ₃ H ₇ ), dimethylaminomethylene-amino (N = CH-N (CH ₃ ) ₂ ), or diethylaminomethylene-amino (N = CH-N (C ₂ H ₅ ) ₂ ).

n very particularly preferably stands for the numbers 0 or 1.

R, ι very particularly preferably represents fluorine, chlorine, bromine or methyl, ethyl, methoxy or ethoxy which is optionally substituted by fluorine or chlorine.

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

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

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

R ⁵ very particularly preferably represents hydrogen, formyl, methyl or

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

The grouping N (R ⁴ R ⁵ ) very particularly preferably also represents dimethylaminomethyleneamino (N = CH-N (CH ₃ ) ₂ ).

R ¹ most preferably represents fluorine, chlorine or methyl or methoxy which is optionally substituted by fluorine.

R ² most preferably represents methyl or ethyl.

R most preferably represents 1-fluoroeth-1-yl or 2-fluoro-prop-2-yl.

R most preferably represents hydrogen.

R> 5 most preferably represents hydrogen or formyl.

The general or preferred radical definitions listed above apply both to the end products of the formula (I) and correspondingly to the starting or intermediate products required in each case for the preparation. This

Residual definitions can be combined with one another, that is, also between the specified preferred ranges.

Preferred compounds according to the invention are those of the formula (I) in which a combination of those listed above as preferred (“preferably”)

Meanings exist.

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 as most preferred above.

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) and to the mixtures of these isomeric compounds.

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

in which

n, R 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 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, to carry out further conversions by customary methods.

If, for example, l- (l-benzothiazol-2-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), n, R ¹ , R ² , R ⁴ and R ⁵ preferably have those meanings which are preferred for n, R ¹ , R above in connection with the description of the compounds of the general formula (I) according to the invention ² , R ⁴ and R ^{5 have been} specified.

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 benzthiazolylalkylamines of the general formula (IV)

in which

n, R and R ^ have the meaning given above, - and / or acid adducts of compounds of the general formula (IV), such as, for example, the hydrochlorides -

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

optionally in the presence of a reaction auxiliary, e.g. Hydrogen chloride, and optionally in the presence of a diluent, e.g. n-decane or 1,2-dichlorobenzene, at temperatures between 100 ° C and 200 ° C (see

Manufacturing 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 benzothiazolylalkylamines of the general formula (IV) required as precursors are known and / or can be prepared by processes known per se (cf. WO-A-96/04252).

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 ³ preferably has the meaning already given above in connection with the description of the compounds of the general invention

Formula (I) has been indicated as preferred or 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 the preparation of the compounds of the general formula (I) is preferably carried out using a diluent. In addition to water, suitable diluents for carrying out the process according to the invention are, above all, inert organic solvents. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane,

Chloroform, carbon tetrachloride; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones, such as acetone, butanone or methyl isobutyl ketone; Nitriles, such as acetonitrile, propionitrile or butyronitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid 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, their mixtures with water or pure water.

The usual inorganic or organic bases or acid acceptors are generally suitable as reaction aids for the process according to the invention. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkanolates, such as sodium, potassium or calcium acetate, lithium, sodium, potassium or calcium amide, sodium, potassium or calcium carbonate, sodium, potassium or calcium hydrogen carbonate, lithium, sodium, potassium or calcium hydride, lithium, sodium, potassium or calcium hydroxide, sodium or potassium - - methanolate, -ethanolate, -n- or -i-propanolate, -n-, -i-, -s- or -t-butanolate; 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-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-ene (DBU).

The reaction temperatures can be varied within a substantial range when carrying out the process according to the invention for the preparation of the triazines.

In general, temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 120 ° C.

The process according to the invention for the preparation of the triazines is generally carried out under normal pressure. However, it is also possible to use the invention

Process under increased or reduced pressure - generally between 0.1 bar and 10 bar.

To carry out the process according to the invention for the preparation of the triazines, 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 processing 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 understood to mean all plants that grow in places grow 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 with the following plants:

Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduippum, Sonuanum , Rotala, Lindernia, Lamium, Veronica, Nbutlon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis,

Brassica, lactuca, cucumis, cucurbita.

Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis,

Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopeeurus, Apera, Aegilops, Phalaris.

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

According to the invention, all plants and parts of plants can be treated. Plants are understood here to mean all plants and plant populations, such as desired and unwanted wild plants or crop plants (including naturally occurring crop plants). Cultivated plants can be plants that are grown by conventional breeding and optimization methods or by Biotechnological and genetic engineering methods of combinations of these methods can be obtained, including the transgenic plants and including the plant varieties which can or cannot be protected by plant breeders' rights. Plant parts are to be understood to mean all above-ground and underground parts and organs of plants, such as shoots, leaves 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 propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.

The treatment of the plants and plant parts and plant parts with the active compounds according to the invention is carried out directly or by acting on their surroundings, living space or storage space according to the usual treatment methods, e.g. by dipping, spraying, vaporizing, atomizing, scattering, spreading and, in the case of propagation material, in particular in the case of seeds, furthermore by single- or multi-layer coating.

However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants.

Depending on the concentration, the active compounds according to the invention are suitable for combating total weeds, e.g. on industrial and track systems and on paths and squares with and without tree cover. Likewise, the active compounds according to the invention for weed control in permanent crops, e.g. Forest, ornamental,

Fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants, used 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 and a broad spectrum of activity when used on the soil and on aerial parts of plants. To a certain extent, they are also suitable for the selective control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops, both in the pre-emergence and in the post-emergence process.

The active ingredients can be overfilled in 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 and 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, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as

Chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

The following are suitable as solid carriers: for example ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, are suitable as solid carriers for granules Question: eg broken and fractionated natural rocks such as calcite, Marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; Possible emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example

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

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

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

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

The active compounds according to the invention, as such or in their formulations, can also be used for combating weeds, in a mixture with known herbicides, finished formulations or tank mixes being 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), Bentazon, Benzobicyclon, Benzofenap, Benzoylprop (-ethyl), Bialaphos, Bifenox, Bispyribac (- sodium), Bromobutide, Bromofenoxim, Bromoxynil, Butachlor, Butroxydim, latex, Cafenstrole, Caloxydim, Carbetamide, Carfentrazone (-ethyl), Chlomethoxyfen, Chloramben, Chloridazon, Chlorimuron (-ethyl), Chlornitrofen, Chlorsulfuron, Chlorotoluron, Cinidon (-ethyl), Cinmethylin, Cinosulfuron, Cleimoxydim, Clethod dinafop (-propargyl), Clomazone, Clomeprop, Clopyralid, Clopyrasulfuron (-methyl), Cloransulam (-methyl), Cumyluron, Cyanazine, Cybutryne, Cycloate, Cyclosulfam-uron, Cycloxydim, Cyhalofop (-butyl), 2,4-D, 2,4-D, 2,4-DB, 2,4-DP, desmedipham, dialate, dicamba, diclofop (-methyl), diclosulam, diethatyl (-ethyl), difenzoquat, diflufican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, Dimethenamid, Dimexyflam, Dinitramine, Diphenamid, Diquat, Dithiopyr, Diuron, Dymron, Epropodan, EPTC, Esprocarb, Eth alfluralin, ethametsulfuron (-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanide, fenoxaprop (-P-ethyl), fentrazamide, flamprop (-isopropyl), flamprop (-isopropyl-L), flamprop (-methyl),

Flazasulftiron, Florasulam, Fluazifop (-P-butyl), Fluazolate, Flucarbazone, Flufenacet, Flumetsulam, Flumiclorac (-pentyl), Flumioxazin, Flumipropyn, Flumetsulam, Fluometuron, Fluorochloridone, Fluoroglycofen (-ethyl), Flupetsilam- sulfuron (-methyl, -sodium), flurenol (-butyl), fluridone, fluroxypyr (-meptyl), flur-primidol, flurtamone, fluthiacet (-methyl), fluthiamide, fomesafen, glufosinate (- ammonium), glyphosate (-isopropylammonium) , Halosafen, Haloxyfop (-erhoxy-ethyl), Haloxyfop (-P-methyl), Hexazinone, Imazamethabenz (-methyl), Imazamethapyr, Imazamox, Imazapic, Imazapyr, Imazaquin, Imazethapyr, Imazosulfuron, Iodosulfonon (-methyl, -sodium), Ioxynil, Isopropalin, Isoproturon, Isouron, Isoxaben, Isoxachlortole, Isoxaflutole, Isoxapyrifop, Lactofen, Lenacil, Linuron, MCPA,

MCPP, Mefenacet, Mesotrione, Metamitron, Metazachlor, Methabenzthiazuron, Metobenzuron, Metobromuron, (alpha-) Metolachlor, Metosulam, Metoxuron, Metribuzin, Metsulfuron (-methyl), Molinate, Monolinuron, Nicroanulfononon, Napropur Orbencarb, Oryzalin, Oxadiargyl, Oxadiazon, Oxasulfuron, Oxaziclomefone, Oxyfluorfen, Paraquat, Pelargonic acid, Pendimethalin,

Pendralin, Pentoxazone, Phenmedipham, Piperophos, Pretilachlor, Primi sulfuron (- methyl), Prometryn, Propachlor, Propanil, Propaquizafop, Propisochlor, Propyz- amide, Prosulfocarb, Prosulfuron, Pyraflufen (-ethyl), Pyrazolate, Pyrazosulfuron (- ethyl), Pyrazoxyfen, Pyribenzoxim, Pyributicarb, Pyridate, Pyrefimobac (pyrimidobac) (-sodium), Quinchlorac, Quinmerac, Quinoclamine, Quizalofop (-P-ethyl), Quizalofop (-P-tefuryl), Rimsulfuron, Sethoxydim, Simazine, Simetryn, Sulcotrione,

Sulfentrazone, sulfometuron (-methyl), sulfosate, sulfosulfuron, tebutam, tebutihuron, tepraloxydim, terbuthylazine, terbutryn, thenylchlor, thiafluamides, thiazo-pyr, thidiazimin, thifensulfuron (-methyl), triobenilulfonalloxyl, carboxate, tiobarbyn, triobencarbon, carboxate Tribenuron (methyl), triclopyr, tridiphane, trifluralin and triflusulfuron.

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. Likewise, the use of compounds which improve crop plant tolerance (iofenes) in

To mention connection with the compounds of the invention as advantageous.

The active ingredients as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use

Solutions, suspensions, emulsions, powders, pastes and granules are used. They are used in the usual way, e.g. by pouring, spraying, spraying, sprinkling.

The active compounds according to the invention can be applied both before and after 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 effort is 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.

Manufacturing examples

example 1

1.2 g (10 mmol) of 2-fluoro-isobutyric acid methyl ester are at room temperature (approx.

20 ° C.) with stirring to a mixture of 3.0 g (10 mmol) of l- (l-benzothiazol-2-yl-ethyl) -biguanide hydrochloride (racemic), 0.55 g (10 mmol) of sodium methylate and 40 added ml of methanol. The reaction mixture is stirred at room temperature for 18 hours, then added to approximately the same volume of water and extracted with methylene chloride. The organic extraction solution is washed with water, dried with sodium sulfate and filtered. The filtrate is concentrated in a water jet vacuum, the residue is digested with ligroin and the crystalline product is isolated by suction.

0.20 g (6% of theory) of 2-amino-4- (l-fluoro-l-methyl-ethyl) -6 - [(l-benzothiazol-2-yl) ethylamino] -l are obtained, 3,5-triazine (racemate) with a melting point of 188 ° C.

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)

Starting materials of formula (II)

Example (IM

A mixture of 6.3 g (29 mmol) of l- (benzothiazol-2-yl) ethylamine and 2.4 g (29 mmol) of cyanoguanidine is heated to a (bath) temperature of 160 ° C. A melt forms after approx. 30 minutes. After a further 30 minutes, the heating bath is removed and, after cooling to room temperature, the crude product is digested with diethyl ether and the crystalline product is isolated by suction.

6.0 g (69% of theory) of 1- (benzothiazol-2-yl) ethyl biguanide are obtained as a solid product, which can be used without further purification to prepare compounds of the general formula (I).

Analogously to Example II-1, for example, the compounds of the general formula (I) listed in Table 2 below can also be prepared.

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

Examples of use:

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 about 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 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 annihilation

In this test, for example, the compounds according to Preparation Examples 1 and 2, with good tolerance to crop plants, such as cotton, corn and wheat, show a strong action against weeds.

Example B

Post emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

Test plants with 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.

It means:

0% = no effect (like untreated control) 100% = total destruction

In this test, for example, the compounds according to Preparation Examples 1 and 2 show a strong action against weeds. Table B1: Post emergence test / greenhouse

Claims

claims

1. Substituted benzothiazolylalkylamino-l, 3,5-triazines of the general formula

(I)

in which

n stands for the numbers 0, 1, 2, 3 or 4,

R ^{1 represents} nitro, cyano, carbamoyl, thiocarbamoyl, halogen or alkyl or alkoxy each optionally substituted by cyano, halogen or C 1 -C ₄ -alkoxy, each having 1 to 6 carbon atoms,

R represents alkyl with 1 to 6 carbon atoms optionally substituted by cyano, halogen or C] -C - alkoxy or represents cycloalkyl with 3 to 6 carbon atoms optionally substituted by cyano, halogen or C 1 -C ₄ alkyl,

R ³ for hydrogen, for halogen, for by cyano, halogen, hydroxy, Cj-

C ₄ - Alkoxy or Cι-C ₄ alkylthio substituted alkyl having 1 to 6 carbon atoms, each for alkylcarbonyl, alkoxycarbonyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each substituted by cyano, halogen or Cι-C ₄ - alkoxy, each having 1 to 6 Carbon atoms in the alkyl groups, for each optionally by

Halogen substituted alkenyl or alkynyl each having 2 to 6 carbon atoms, or for optionally by cyano, halogen or C 1 -C 4 -alkyl-substituted cycloalkyl having 3 to 6 carbon atoms,

R represents hydrogen or alkyl which has 1 to 6 carbon atoms and is optionally substituted by cyano, halogen or -CC alkoxy, and

R for hydrogen, for formyl or for each optionally by

Cyano, halogen or C1-C4-alkoxy substituted alkyl, alkylcarbonyl, alkoxycarbonyl or alkylaminocarbonyl, each with 1 to 6

Carbon atoms in the alkyl groups,

or the N (R ⁴ R ³ ) group also represents alkylaminoalkylidene amino or dialkylaminoalkylidene amino each having up to 6 carbon atoms in the alkyl groups or alkylidene groups.

Substituted benzthiazolylalkylamino-l, 3,5-triazines according to claim 1, characterized in that

n for the numbers 0, 1,

2 or 3 stands,

R ¹ for nitro, cyano, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, iodine or for alkyl or alkoxy each substituted by cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i-propoxy, each with 1 to 5 Carbon atoms,

R ² for alkyl optionally substituted by cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i-propoxy alkyl having 1 to 5 carbon atoms or for cycloalkyl optionally substituted by cyano, fluorine, chlorine, bromine, methyl or ethyl having 3 to 6 carbon atoms, R .3 for hydrogen, for fluorine, chlorine, bromine, for cyano, fluorine,

Chlorine, bromine, hydroxyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio substituted alkyl having 1 to 5 carbon atoms, each optionally substituted by cyano, fluorine,

Chlorine, methoxy, ethoxy, n- or i-propoxy-substituted alkylcarbonyl, alkoxycarbonyl, alkoxy, alkylthio, alkylsulfmyl or alkylsulfonyl each having 1 to 5 carbon atoms in the alkyl groups, for alkenyl or alkynyl optionally substituted by fluorine, chlorine or bromine each has 3 to 5 carbon atoms, or represents cycloalkyl having 3 to 6 carbon atoms which is optionally substituted by cyano, fluorine, chlorine, bromine, methyl or ethyl,

R _> 4 represents hydrogen or alkyl having 1 to 5 carbon atoms which is optionally substituted by cyano, fluorine, chlorine, bromine, methoxy or ethoxy,

, s

R ^"stands for hydrogen, for formyl or for alkyl, alkylcarbonyl, alkoxycarbonyl or alkylaminocarbonyl, each of which has 1 to 5 carbon atoms in the alkyl groups, optionally substituted by cyano, fluorine, chlorine, bromine, methoxy or ethoxy, or

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

3. Substituted benzothiazolylalkylamino-l, 3,5-triazines according to Anspmch 1 or 2, characterized in that

n represents the numbers 0, 1 or 2, R for nitro; Cyano, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, or represents methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,

R for each optionally by cyano, fluorine, chlorine, methoxy or

Ethoxy substituted methyl, ethyl, n- or i-propyl, n-, i- or s-

Butyl, or for each optionally by cyano, fluorine, chlorine,

Bromine, methyl or ethyl substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,

R for hydrogen, for fluorine, chlorine, bromine, for methyl, ethyl, n- or i-propyl, n-, i- or s substituted by cyano, fluorine, chlorine, bromine, hydroxy, methoxy, ethoxy, methylthio or ethylthio - Butyl, for each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl , Methylsulfonyl or ethylsulfonyl, for propenyl, butenyl, propynyl or optionally substituted in each case by fluorine, chlorine or bromine

Butynyl, or cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, which is in each case optionally substituted by cyano, fluorine, chlorine, bromine, methyl or ethyl,

R ^{4 is} hydrogen or is optionally by cyano, fluorine,

Chlorine, bromine, methoxy or ethoxy substituted methyl, ethyl, n- or i-propyl,

R ⁵ for hydrogen, for formyl or for each optionally substituted by cyano, fluorine, chlorine, bromine, methoxy or ethoxy

Methyl, ethyl, n- or i-propyl, acetyl, propionyl, n- or i-butyroyl, Methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, E hylaminocarbonyl, n- or i-propylaminocarbonyl, or

the grouping N (R ⁴ R ⁵ ) for methylaminomethyleneamino (N = CH- NHCH ₃ ), ethylaminomethyleneamino (N = CH-NHC ₂ H ₅ ), n- or i-propylaminomethyleneamino (N = CH-NHC H ₇ ), dimethylaminomethylene- amino (N = CH-N (CH ₃ ) ₂ ), or diethylaminomethylene amino (N = CH-N (C ₂ H ₅ ) ₂ ).

4. Substituted benzothiazolylalkylamino-l, 3,5-triazines according to any one of claims 1 to 3, characterized in that

n represents the numbers 0 or 1,

R represents fluorine, chlorine, bromine or methyl, ethyl, methoxy or ethoxy which is optionally substituted by fluorine or chlorine,

R ^"represents in each case methyl, ethyl, n- or i-propyl optionally substituted by fluorine or chlorine,

R ^" represents methyl, ethyl, n- or i-propyl, each substituted by fluorine or chlorine,

R ^{4 represents} hydrogen, methyl or ethyl,

R ^{5 stands} for hydrogen, for formyl, for methyl or ethyl, or for in each case optionally substituted by fluorine, chlorine, methoxy or ethoxy, acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl, or the grouping N (R ⁴ R ⁵ ) represents dimethylaminomethyleneamino (N = CH-N (CH ₃ ) ₂ ).

5. Substituted benzothiazolylalkylamino-l, 3,5-triazines according to any one of claims 1 to 4, characterized in that

R ¹ for fluorine, chlorine or for each optionally by fluorine or

Chlorine substituted methyl or methoxy,

R ^{2 represents} methyl or ethyl,

R represents 1-fluoroeth-1-yl or 2-fluoroprop-2-yl,

R represents hydrogen,

R ^{5 represents} hydrogen or formyl.

6. A process for the preparation of substituted benzothiazolylalkylamino-1,3,5-triazines according to any one of claims 1 to 4, characterized in that

Biguanides of the general formula (II)

in which

n, Rl, R ² , R ⁴ and R ^{5 have} the meaning given in one of claims 1 to 5,

and / or acid adducts of compounds of the general formula (II) with alkoxycarbonyl compounds of the general formula (III)

R -CO-OR '(III)

in which

R has the meaning given in one of claims 1 to 5 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 can be carried out on the compounds of the general formula (I) thus obtained as part of the definition of the substituent by customary methods.

7. Biguanides of the general formula II

in which

n, Rl, R ² , R4 and R ^ have the meaning given in one of claims 1 to 5.

8. A process for the preparation of substituted biguanides according to claim 7, characterized in that benzothiazolylalkylamines of the general formula (IV)

in which

n, Rl and R ^{2 have} the meaning given in one of claims 1 to 5,

- and / or acid adducts of compounds of the general formula (IV),

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

if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent at temperatures between 100 ° C. and 200 ° C.

9. A method for controlling unwanted plants, characterized in that at least one compound according to one of claims 1 to 5 is allowed to act on the plants and / or their habitat.

10. Use of at least one compound according to one of claims 1 to 5 for controlling unwanted plants.

11. Herbicidal agent, characterized by a content of a compound according to one of claims 1 to 5 and conventional extenders and / or surface-active agents.