WO2000078737A2

WO2000078737A2 - Aryloxy ethylamino triazines as herbicides

Info

Publication number: WO2000078737A2
Application number: PCT/EP2000/005115
Authority: WO
Inventors: Stefan Lehr; Kristian Kather; Hans-Jochem Riebel; Katharina Voigt; Mark Wilhelm Drewes; Peter Dahmen; Dieter Feucht; Rolf Pontzen
Original assignee: Bayer Aktiengesellschaft
Priority date: 1999-06-17
Filing date: 2000-06-05
Publication date: 2000-12-28
Also published as: DE19927611A1; AU5401800A; WO2000078737A3

Abstract

The invention relates to novel aryloxy ethylamino triazines of general formula (I) in which n, R?1, R2, R3¿ and Z have the meanings cited in the description, whereby compounds N-[4-amino-6- (1-fluoro-1- methyl-ethyl) -1,3,5-triazine-2-yl] -N-(2-phenoxy-ethyl) -amine, N-[4-amino-6- (1-fluoro -1-methyl -ethyl)- 1,3,5 -triazine -2-yl] -N-[2- (3,5- difluoro -phenoxy) -ethyl] -amine, N-[4-amino-6-(1-fluoro- 1-methyl- ethyl)- 1,3,5- triazine- 2-yl]-N-[2-(3,5-dimethyl- phenoxy) -ethyl]- amine (cf. WO -A-98/34925) are excluded by d isclaimers. The invention also relates to methods for producing said aryloxy ethylamino triazines, and to their use as herbicides. The invention additionally relates to the use of the compounds of general formula (I) including the compounds excluded per disclaimer as selective herbicides in treating cotton, barley, corn, beet and wheat crops.

Description

Aryloxyethylaminotriazines

The invention relates to new aryloxyethylaminotriazines, a process and new intermediates for their preparation and the use of new and known aryloxyethylaminotriazines as selective herbicides.

Some aryloxyethylaminotriazines, namely the compounds N- [4-amino-6- (l-fluoro-l-methyl-ethyl) -l, 3,5-triazin-2-yl] -N- (2-phenoxy-ethyl) -amin, N- [4-amino-6- (l-luor-l-methyl-ethyl) -l, 3,5-triazin-2-yl] -N- [2- (3,5-difluorophenoxy ) -ethyl] -amine,

N- [4-amino-6- (l-fluoro-l-methyl-ethyl) -l, 3,5-triazin-2-yl] -N- [2- (3,5-dimethyl-phenoxy) -ethyl] -amine, have already been mentioned as potential herbicides by way of example in a patent application (cf. WO-A-98/34925). However, the possible uses of these connections are not described in detail.

New aryloxyethylaminotriazines of the general formula (I)

in which

n represents the numbers 0, 1, 2 or 3,

R for nitro, cyano, carbamoyl, thiocarbamoyl, hydroxy, halogen, phenyl,

Phenoxy, or for alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, dialkylaminocarbonyl or dialkylamino sulfonyl, each with 1 to 6 carbon atoms in the alkyl groups, each optionally substituted by cyano, halogen or C ₄ -C alkoxy stands, or - in the event that n is greater than 1 - also together with an adjacent second radical R ^{1 represents} a benzo group,

R "represents hydrogen or alkyl having 1 to 6 carbon atoms,

R represents hydrogen, formyl or, in each case optionally by cyano,

Halogen or C 1 -C ₄ -alkoxy-substituted alkyl, alkylcarbonyl, alkoxycarbonyl or alkylaminocarbonyl each having 1 to 6 carbon atoms in the alkyl groups,

or the grouping N (R R) also represents dialkylammoalkydenamino having up to 6 carbon atoms in the alkyl groups, and

Z represents alkyl with 1 to 6 carbon atoms which is optionally substituted by hydroxy, cyano, halogen or C] -C ₄ -alkoxy,

the compounds N- [4-ammo-6- (l-fluoro-l-methyl-ethyl) -l, 3,5-tπazιn-2-yl] -N- (2-phenoxy-ethyl) -amιn, N- [4-amino-6- (l-fluoro-l-methyl-ethyl) -l, 3,5-tnazion-2-yl] -N- [2- (3,5-difluorophenoxy) ethyl ] -amιn, N- [4- amino-6- (1-fluoro-1-methyl-ethyl) - l, 3,5-tπazιn-2-yl] -N- [2- (3,5-dimethyl- phenoxy) ethyl] -amm (see WO-A-

98/34925) are excluded by disclaimer -

found

It was further found that the aryloxyethylaminotriazines of the general formula

(I) can be used particularly well for the selective control of weeds

The stand out

lo \ yethylamιnotπazιne of the general formula (I) and also those exempted above by Disclaimei

Connections - by surprising protection of selected crops in different Crops from. Preferred substituents or ranges of the radicals present in the formulas listed above and below are described below.

R ¹ preferably represents nitro, cyano, carbamoyl, thiocarbamoyl, hydroxy,

Fluorine, chlorine, bromine, iodine, phenyl, phenoxy, or for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy , Methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl , Ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, di - methylamino, diethylamino, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, dimethylaminosulfonyl or diethylaminosulfonyl, or - in the event that n is larger than 1 is - also together with an adjacent second radical R ¹ for a benzo group.

R ² preferably represents hydrogen, methyl, ethyl, n- or i-propyl.

R preferably represents hydrogen, formyl or, if appropriate, in each case

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, ethyl aminocarbonyl, n - or i-Propylaminocarbonyl, or the grouping

N (RR ³ ) also preferably represents dimethylaminomethyleneamino or diethylaminomethyleneamino.

Z preferably represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl optionally substituted by hydroxy, cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i-propoxy . R particularly preferably represents nitro, cyano, fluorine, chlorine, bromine, phenyl, phenoxy, or methyl, ethyl, n- or i-propyl, n-, i-, s- or optionally substituted by fluorine and / or chlorine t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio,

Methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, methylamino, ethylamino, n- or i-propylamino, dimethylamino, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, dimethylaminocarbonon or dimethylaminosulfonyl or dimethylaminosulfonyl or dimethylaminosulfonyl or dimethylaminosulfonyl or the case that n is greater than 1 - also together with an adjacent second radical R ¹ for a benzo group.

R ^" particularly preferably represents hydrogen or methyl.

R ³ particularly preferably represents hydrogen, formyl or methyl, ethyl, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, optionally substituted by fluorine, chlorine, methoxy or ethoxy, Ethylamino-carbonyl, n- or i-propylaminocarbonyl, or the grouping N (RR) also preferably represents dimethylaminomethyleneamino or diethylamino-methylenamino.

Z particularly preferably represents optionally by hydroxy, cyano, fluorine,

Chlorine, bromine, methoxy, ethoxy, n- or i-propoxy substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl.

R ¹ very particularly preferably represents nitro, cyano, fluorine, chlorine, bromine, phenoxy or methyl, ethyl, n- or i-propyl, n-, i-, s- or t- which is optionally substituted by fluorine and or chlorine. Butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, Ethylsulfinyl, methylsulfonyl, ethylsulfonyl, dimethylamino, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl or dimethylaminocarbonyl.

R ² very particularly preferably represents hydrogen.

R ³ very particularly preferably stands for hydrogen, formyl, acetyl, propionyl, M Meetthhooxxyyccaarrbboonnyyll ooddeerr EEtthhooxxyyccaarrbboonnyyll ,, ooddeerr ddiiee (grouping N (RR) also preferably stands for dimethylaminomethyleneamino.

Z particularly preferably represents optionally by fluorine, chlorine, bromine,

Methoxy or ethoxy substituted methyl, ethyl, n- or i-propyl.

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 there is a combination of the meanings listed above as preferred.

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

Optionally substituted radicals can be mono- or polysubstituted, with multiple substitution the substituents can be the same or different.

Examples of the compounds of the general formula (I) according to the invention are tabulated below:

The aryloxyethylaminotriazines of the general formula (I) are obtained if aryloxyethylbiguanides of the general formula (II)

in which

n, R ¹ , R ² and R ^{3 have} the meaning given above,

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

with alkoxycarbonyl compounds of the general formula (III) Z-CO-OR '(III) in which

Z has the meaning given above and

R 'represents alkyl, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,

and optionally on the compounds of the general formula (I) thus obtained, as part of the definition of the substituent, carries out further conversions by customary methods.

If, for example, 1- [2- (2-fluorophenoxy) ethyl] biguanide and 2-chloropropanoic acid methyl ester are used as starting materials, the course of the reaction in the process according to the invention can be sketched using the following formula:

Formula (II) provides a general definition of the aryloxyethyl biguanides 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 (II), n, R, R ^~ and R preferably or in particular have those meanings which have already been described above in connection with the description of the compounds of the general formula (I) according to the invention preferably or as particularly preferred for n, R. ¹ , R ² and R ^{3 have been} specified. Suitable acid adducts of compounds of the formula (II) are their addition products with protonic acids, such as, for example, 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 aryloxyethyl biguanides of the general formula (II) are obtained if aryloxyethyl amines of the general formula (IV)

in which

n 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)

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 aryloxyethylammes of the general formula (IV) required as precursors are known and / or can be prepared by processes known per se (cf. J. Am. Chem. Soc. 109 (1987), 4036-4046; J. Chem. Soc. 1933, 270-273; J. Heterocycl. Chem. 19 (1982), 537-539; J. Med. Chem. 6 (1963), 705-711).

The aryloxyethylammes of the general formula (IV) are obtained, for example, if aryloxyacetonitriles of the general formula (VI)

in which

n and R have the meaning given above,

with hydrogenating agents, e.g. Lithium aluminum hydride (LiAlH) or diisobutyl aluminum hydride, optionally in the presence of a diluent, e.g. Toluene, at temperatures between 0 ° C and 150 ° C (see. The manufacturing examples).

The aryloxyacetonitriles of the general formula (VI) to be used as precursors can be reacted with hydroxyarenes of the general formula (VII)

in which n and R ^{1 have} the meaning given above,

- or of their alkali metal salts -

with chloroacetonitrile, optionally in the presence of an acid acceptor, e.g. Potassium carbonate, optionally in the presence of a reaction auxiliary, e.g. Sodium iodide, and optionally in the presence of a diluent, e.g. Acetone can be produced at temperatures between 0 ° C and 100 ° C (see the 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 compounds of the general formula (I). In the general formula (III), Z preferably or in particular has the meaning which has already been mentioned above in connection with the description of the compounds of the general formula (I) according to the invention preferably or as being particularly preferred for Z; 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, tetrahydrof ran 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, ethyldiisopropylamine, N, N-dimethylcyclohexylamine, dicyclohexylamine, ethyldicyclohexylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, Pyridine, 2-methyl, 3-methyl, 4-methyl, 2,4-dimethyl, 2,6-dimethyl, 3,4-dimethyl and 3,5-dimethyl-pyridine, 5- Ethyl 2-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-enes (DBU).

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. Working up is carried out according to customary methods (cf. the production examples).

The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers. 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, Lamium, Lammium Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.

Dicotyledon cultures of the genera: Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon,

Nicotiana, Phaseolus, Pisum, Solanum, Vicia.

Monocotyledonous weeds of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochlo

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 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, for example on industrial and rail tracks and on paths and squares with and without tree growth. Likewise, the active compounds according to the invention for weed control in permanent crops, for example forest, ornamental trees, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa and berry fruit and hop plants, on ornamental and sports turf and pastures as well as 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. They are particularly suitable for the selective control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops, both pre-emergence and post-emergence.

The compounds of the formula (I) and the compounds excluded by disclaimer are well tolerated by a number of crop plants, in particular cotton, barley, maize, beet and wheat, and can also be used selectively in these crops Combat

Weeds are used.

The possibility of using the compounds of the formula (I) and the compounds excluded by disclaimer for selective weed control in beets - feed beet and sugar beet - is to be emphasized particularly since most

Herbicides in the usual application rates of beets are not tolerated.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active substance-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, ie liquid solvents and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents.

If water is used as an extender, e.g. also organic

Solvents are used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or alkyl naphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, 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 as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust,

Coconut shells, corn cobs and tobacco stems; 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 waste liquor and

Methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, 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 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), bentazone, benzobicyclone, benzofenap, benzoylprop (-ethyl), bialaphos, bifenox, bispyribac (- sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butroxydim, butylate, cafenstrole, caloxydiment, carbraamide, ethyl), chloromethoxyfen, chloramben, chloridazon, chlorimuron (-ethyl), chloronitrofen, chlorosulfuron, chlorotoluron, cinidon (-ethyl), cinmethylin, cinosulfuron, clefoxydim, clethodim, clodinafop (-propargyl), clomazone, clomeprop , Clopyra-sulfuron (-methyl), Cloransulam (-methyl), Cumyluron, Cyanazines, Cybutryne, Cycloate, Cyclosulfamuron, Cycloxydim, Cyhalofop (-butyl), 2,4-D, 2,4-DB, 2,4-DP , Desmedipham, Diallate, Dicamba, Diclofop (-methyl), Diclosulam, Diethatyl (-ethyl ), Difenzoquat, Diflufenican, Diflufenzopyr, Dimefuron, Dimepiperate, Dimethachlor, Dimeffiametryn, Dimethenamid, Dimexyflam, Dinitramine, Diphenamid, Diquat, Dithiopyr, Diuron, Dymron, Epropodan, EPTC, Esprocuron, Ethamets-Ethrocarbon, Ethamets Ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanide, fenoxaprop- (-P-ethyl), fentrazamide, flamprop (-isopropyl), flamprop (-isopropyl-L), flamprop (- methyl), flazasulfuron, florasulam, fluazifop (-P-butyl) , Fluazolate, Flucarbazone, Flufenacet, Flumetsulam, Flumiclorac (-pentyl), Flumioxazin, Flumipropyn, Flumet- sulam, Fluometuron, Fluorochloridone, Fluoroglycofen (-ethyl), Flupoxam, Fluprop- acil, Flu yrsulfuron (-methyl, -sodium), Flurenol (-butyl), Fluridone, Fluroxypyr (- meptyl), Flurprimidol, Flurtamone, Fluthiacet (-methyl), Fluthiamide, Fomesafen, Glufosinate (-ammonium), Glyphosate (-isopropyl ), Halosafen, Haloxyfop- (-ethoxyethyl), Haloxyfop (-P-methyl), Hexazinone, Imazamethabenz (-methyl), Imazamethapyr, Imazamox, Imazapic, Imazapyr, Imazaquin, Imazethapyr, Imazosulfonon, Iodosulfuron (-methyl, -s ), loxynil, isopropalin, isoproturon, isouron, isoxaben, isoxachlortolc, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, mesotrione, metamitron, metazachlor, methabenzthenzuron, metobromizuron, metobrenzuron, metobrenzuron, metobrenzuron Metosulam, Metoxuron, Metribuzin, Metsulfuron (-methyl), Molinate, Monolinuron, Naproanilide, Naprop- amide, Neburon, Nicosulfuron, Norflurazon, Orbencarb, Oryzalin, Oxadiargyl, Oxadiazon, Oxasulfuron, Oxazicyiomefomarg, Pelaz methalin, pendralin, pentoxazone, phenmedipha m, Piperophos, Pretilachlor, Primisulfuron (-methyl), Prometryn, Propachlor, Propanil, Propaquizafop, Propisochlor, Propyzamide, Prosulfocarb, Prosulfuron, Pyraflufen (-ethyl), Pyrazolate, Pyrazosulfuron (-ethyl), Pyrazoximfen, Pyribenz Pyributicarb, Pyridate, Pyriminobac (- methyl), Pyrithiobac (-sodium), Quinchlorac, Quinmerac, Quinoclamine, Quizalofop- (-P-ethyl), Quizalofop (-P-tefuryl), Rimsulfuron, Sethoxydim, Simazine, Simetrynent, Sulraotrione , Sulfometuron (-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim, terbuthylazine, terbutryn, thenylchlor, thifluamamide, thiazopyr, thidiazimin, thifensulfuron (-methyl), thiobencarb, trialkoxydimonuronuron, trialkoxydimonuron (-methyl), triclopyr, tri-diphane, trifluralin and triflusulfuron.

A mixture with other known active ingredients, such as fungicides,

Insecticides, acaricides, nematicides, bird repellants, plant nutrients and soil structure improvers are possible.

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 become. They are used in the customary manner, for example by watering, spraying, spraying or scattering.

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.

Production examples: Example 1

5.64 g (22 mmol) of 1- (2-phenoxy-ethyl) -biguanide hydrochloride are dissolved in 50 ml

Submitted methanol and successively with stirring at 2.degree. C. to 10.degree. C. (ice bath) with 2.37 g (44 mmol) of sodium methylate, 5.5 g of molecular sieve "UOP type 3A" (drying agent) and with 2.94 g (23 mmol) of trifluoroacetic acid The reaction mixture is stirred in a thawing ice bath overnight (about 15 hours). After removing the molecular sieve by filtration, the filtrate is concentrated under reduced pressure, diluted to about twice the volume with water, neutralized with 2N hydrochloric acid and then The organic phase is washed with water, dried with sodium sulfate and filtered, and the solvent is carefully distilled off from the filtrate under reduced pressure.

0.50 g (7% of theory) of N- (4-amino-6-trifluoromethyl-l, 3,5-triazin-2-yl) -N- (2-phenoxy-efhyl) amine is obtained as a solid residue .

logP (at pH 7.5): 2.45.

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

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 V.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 ^b) .

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

Retention times by linear interpolation between two consecutive alkanones). The lambda max values were determined using the UV spectra from 200 nm to 400 nm in the maxima of the chromatographic signals.

The compound listed above in Table 1 as Example 5 can be produced, for example, as follows:

A mixture of 1.0 g (3.4 mmol) of N- [4-amino-6- (l-fluoro-l-methyl-ethyl) -l, 3,5-triazin-2-yl] -N- ( 2-phenoxy-ethyl) amine, 0.52 g (4.1 mmol) of N, N-dimethylformamide-dimethylacetal (94%) and 30 ml of 1,4-dioxane is stirred for 18 hours at room temperature (approx 20 ° C.) and then concentrated in a water jet vacuum. The residue is stirred with water for 30 minutes and then shaken with ethyl acetate. The organic phase is then dried with sodium sulfate and filtered. The solvent is carefully distilled off from the filtrate under reduced pressure.

0.50 g (42% of theory) of N- [4-dimethylaminomethyleneamino-6- (l-fluoro-l-methyl-ethyl) -l, 3,5-triazin-2-yl] -N- (2nd -phenoxy-ethyl) -amine as residue.

For example, the compound listed above in Table 1 as Example 16 can be made as follows:

A mixture of 0.50 g (1.54 mmol) of N- [4-amino-6- (l-fluoro-l-methyl-ethyl) -1,3,5-triazin-2-yl] -N- [ 2- (4-chlorophenoxy) ethyl] amine and 10 ml acetic anhydride is stirred for 20 hours at room temperature (approx. 20 ° C) and then for a further 60 minutes at 60 ° C. The mixture is then concentrated under reduced pressure and the residue is shaken with saturated aqueous sodium bicarbonate solution / dichloromethane. The organic phase is washed with saturated aqueous sodium hydrogen carbonate solution, then dried with sodium sulfate and filtered. The solvent is carefully distilled off from the filtrate under reduced pressure.

0.35 g (62% of theory) of N- [4-acetylamino-6- (l-fluoro-l-methyl-ethyl) -1,3,5-triazin-2-yl] -N- [2 - (4-chlorophenoxy) ethyl] amine as residue.

Starting materials of formula (II): Example (II-l)

7.6 g (44 mmol) of 2-phenoxyethylamine hydrochloride and 3.7 g (44 mmol) of cyano-guanidine are ground together in a mortar and the mixture is heated to 150 ° C. in a flask. After cooling to about 50 ° C., the volume is made up to 100 ml by adding methanol. The resulting solution can be used directly for the further reaction according to Example 1.

Analogously to Example II-1, it is also possible, for example, to prepare the compounds of the general formula (II) listed in Table 2 below.

Starting materials of the formula (IV): Example (IV-1)

15 g (92 mmol) of 3-methoxy-phenoxyacetonitrile are placed in 500 ml of toluene, 147 ml of an IM solution of diisobutylaluminum hydride in toluene are added and

Stirred at 90 ° C for 3 hours. After adding a further 37.5 ml of an IM solution of diisobutylaluminum hydride in toluene, the mixture is stirred at 90 ° C. for a further 3 hours. After cooling to room temperature, 2N sodium hydroxide solution is carefully added and extracted with ethyl acetate. The organic phase is dried with sodium sulfate and filtered. The solvent is carefully distilled off from the filtrate under reduced pressure.

6.9 g (45% of theory) of 2- (3-methoxyphenoxy) ethylamine are obtained as an oily residue.

logP (at pH 2.3): 0.28

The corresponding hydrochloride can be produced as follows:

4.5 g (27 mmol) of 2- (3-methoxyphenoxy) ethylamine are dissolved in 20 ml of acetone, 20 ml

18% hydrochloric acid and 10 ml of toluene were added and the mixture was concentrated in a water jet vacuum. The residue is concentrated again after taking up in toluene. The remaining residue is triturated with diethyl ether and the crystalline product isolated by suction.

5.4 g (98% of theory) of 2- (3-methoxyphenoxy) ethylamine hydrochloride are obtained. Analogously to Example IV-1, the compounds of the general formula (IV) listed below and the corresponding hydrochlorides can also be prepared, for example.

2-phenoxy-ethylamine, 2- (2-fluorophenoxy) ethylamine, 2- (2-chlorophenoxy) ethylamine, 2- (3-fluorophenoxy) ethylamine, 2- (3-chloro -phenoxy) ethylamine, 2- (4-fluorophenoxy) ethylamine, 2- (4-chlorophenoxy) ethylamine, 2- (2-methylphenoxy) ethylamine, 2- (3-methyl -phenoxy) ethylamine, 2- (4-methylphenoxy) ethylamine, 2- (2-methoxyphenoxy) ethylamine, 2- (4-methoxyphenoxy) ethylamine, 2- (3,5-difluoro phenoxy) ethylamine, 2- (3,5-dimethylphenoxy) ethylamine, 2- (4-phenylphenoxy) ethylamine, 2- (4-phenoxyphenoxy) ethylamine.

Starting materials of the formula (VI): Example (NI-1)

A mixture of 40 g (323 mmol) of 3-methoxyphenol, 30 g (404 mmol) of chloroacetonitrile, 53.5 g (388 mmol) of potassium carbonate, 5 g of sodium iodide and 400 ml of acetone is heated under reflux for 15 hours. After adding a further 6 g of chloroacetonitrile, the mixture is heated under reflux for a further 4 hours and then concentrated in a water jet vacuum. The residue is shaken with methylene chloride / water, the organic phase is separated off, dried with sodium sulfate and filtered. The solvent is carefully distilled off from the filtrate under reduced pressure.

53 g (100%) of theory) of 3-methoxy-phenylacetonitrile are obtained as an amorphous product.

Analogously to Example VI-1, the compounds of the general formula (VI) listed below can also be prepared, for example.

2-phenoxy-acetonitrile, 2- (2-fluorophenoxy) acetonitrile, 2- (2-chlorophenoxy) aceto-nitrile, 2- (3-fluorophenoxy) acetonitrile, 2- (3-chlorine -phenoxy) acetonitrile, 2- (4-fluorophenoxy) acetonitrile, 2- (4-chlorophenoxy) acetonitrile, 2- (2-methylphenoxy) acetonitrile, 2- (3-methyl -phenoxy) acetonitrile, 2- (4-methylphenoxy) acetonitrile, 2- (2-methoxyphenoxy) acetonitrile, 2- (4-methoxyphenoxy) acetonitrile, 2- (3.5-difluorophenoxy ) acetonitrile. 2- (3,5-dimethylphenoxy) acetonitrile, 2- (4-phenylphenoxy) acetonitrile, 2- (4-phenoxyphenoxy) acetonitrile. 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 specified amount is given

Amount of emulsifier and dilute the concentrate 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 destruction

In this test, for example, the compounds according to Preparation Examples 1, 4, 5 and 14, with largely good tolerance to crop plants, such as, for example, cotton, barley, corn, wheat and sugar beet, show a strong action against weeds.

Table A3: Pre emergence test / greenhouse

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 concentration.

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, 2, 3, 4, 5 and 14 show a strong action against weeds.

Table B3: Post emergence test / greenhouse

Claims

claims

1. Compounds of the general formula (I)

in which

n represents the numbers 0, 1, 2 or 3,

R ¹ for nitro, cyano, carbamoyl, thiocarbamoyl, hydroxy, halogen,

Phenyl, phenoxy, or for alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, dialkylaminocarbonyl or dialkylaminosulfonyl, each with 1 to in each case optionally substituted by cyano, halogen or C] -C ₄ -alkoxy 6 carbon atoms in the alkyl groups,

or - in the event that n is greater than 1 - also together with an adjacent second radical R ^{1 represents} a benzo group,

R represents hydrogen or alkyl having 1 to 6 carbon atoms,

R ^{3 represents} hydrogen, formyl or alkyl, alkylcarbonyl, alkoxycarbonyl or alkylaminocarbonyl, each of which has 1 to 6 carbon atoms in the alkyl groups and is optionally substituted by cyano, halogen or -C4-alkoxy, or the grouping N (RR) also represents dialkylammoalkylidene amino having up to 6 carbon atoms in the alkyl groups, and

Z represents alkyl which has 1 to 6 carbon atoms and is optionally substituted by hydroxy, cyano, halogen or C 1 -C ₄ -alkoxy,

the compounds N- [4-amino-6- (l-fluoro-l-methyl-ethyl) -1,3,5-triazin-2-yl] -N- (2-phenoxy-ethyl) amine, N- [4-Amino-6- (l-fluoro-l-methyl-ethyl) -l, 3,5-triazin-2-yl] -N- [2- (3,5-difluorophenoxy) ethyl ] - amine, N- [4-amino-6- (l-fluoro-l-methyl-ethyl) -l, 3,5-triazin-2-yl] -N-

[2- (3,5-dimethyl-phenoxy) -ethyl] amine (cf. WO-A-98/34925) are excluded by disclaimers.

2. Compounds according to claim 1, characterized in that

n represents the numbers 0, 1 or 2,

R for nitro, cyano, carbamoyl, thiocarbamoyl, hydroxy, fluorine, chlorine,

Bromine, iodine, phenyl, phenoxy, or for each methyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,

Ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfmyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, methylamino, ethylamino, n- or i Propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, dimethylaminocarbonyl, diethylamino-carbonyl, dimethylaminosulfonyl or Diethylaminosulfonyl stands, or - in the event that n is greater than 1 - also together with an adjacent second radical R ^{1 represents} a benzo group,

R ^{2 represents} hydrogen, methyl, ethyl, n- or i-propyl,

R ³ for hydrogen, formyl or for methyl, ethyl, n- or i-propyl, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or, in each case optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy i-propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl,

or the grouping N (R R) represents dimethylaminomethylene-amino or diethylaminomethyleneamino, and

Z for optionally by hydroxy, cyano, fluorine, chlorine, bromine,

Methoxy, ethoxy, n- or i-propoxy substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl.

Compounds according to claim 1 or 2, characterized in that

R ¹ for nitro, cyano, fluorine, chlorine, bromine, phenyl, phenoxy, or for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-, each optionally substituted by fluorine and / or chlorine Butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl,

Methylamino, ethylamino, n- or i-propylamino, dimethylamino, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, dimethylaminocarbonyl or dimethylaminosulfonyl, or - in the event that n is greater than 1 - also together with an adjacent second radical R ^{1 represents} a benzo group,

R ^{2 represents} hydrogen or methyl,

R ^{3 represents} hydrogen, formyl or, if appropriate, in each case by fluorine,

Chlorine, methoxy or ethoxy substituted methyl, ethyl, acetyl,

Propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl,

or further the group N (R ² R ³ ) represents dimethylaminomethylene-amino or diethylaminomethyleneamino, and

Z for optionally by hydroxy, cyano, fluorine, chlorine, bromine,

4. Compounds according to any one of claims 1 to 3, characterized in that

R ¹ for nitro, cyano, fluorine, chlorine, bromine, phenoxy or for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy which are each optionally substituted by fluorine and / or chlorine , Ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl,

Ethylsulfinyl, methylsulfonyl, ethylsulfonyl, dimethylamino, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl or dimethylaminocarbonyl,

R ^{2 represents} hydrogen, R ^{3 represents} hydrogen, formyl, acetyl, propionyl, methoxycarbonyl or

Ethoxycarbonyl stands,

or the grouping N (R ² R ³ ) represents dimethylaminomethyleneamino, and

Z represents methyl, ethyl, n- or i-propyl optionally substituted by fluorine, chlorine, bromine, methoxy or ethoxy.

5. A process for the preparation of the compounds according to any one of claims 1 to 4, characterized in that aryloxyethyl biguanides of the general formula (II)

in which

n, R ¹ , R ² and R ^{3 have} the meaning given in one of claims 1 to 4,

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

with alkoxycarbonyl compounds of the general formula (III)

Z-CO-OR '(III) in which

Z has the meaning given in one of claims 1 to 4 and

R 'represents alkyl, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent

and, if appropriate, further conversions are carried out on the compounds of the general formula (I) thus obtained as part of the definition of the substituent by customary methods.

6. Compounds of the general formula (II)

in which

n, R ¹ , R ² and R ^{3 have} the meaning given in one of claims 1 to 4.

7. A method for controlling undesirable plant growth, characterized in that a compound according to one of claims 1 to 4 is allowed to act on undesired plants and their habitat.

8. A method for controlling unwanted vegetation, characterized in that a compound according to one of claims 1 to 4 and / or a compound from the series N- [4-amino-6- (l-fluoro-l-methyl-ethyl ) -l, 3,5-triazin-2-yl] -N- (2-phenoxy-ethyl) -amine, N- [4-amino-6- (l-fluoro-l-methyl-ethyl) -l, 3,5-triazin-2-yl] -N- [2- (3,5-difluorophenoxy) ethyl] amine,

N- [4-amino-6- (l-fluoro-l-methyl-ethyl) -l, 3,5-triazin-2-yl] -N- [2- (3,5-dimethyl-phenoxy) -ethyl] amine in cotton, barley, corn, beet and Wheat crops can affect unwanted plants and their habitat.

9. Use of at least one compound according to one of claims 1 to 4 for controlling unwanted plants.

Use of at least one compound according to one of claims 1 to 4 and or a compound from the series N- [4-amino-6- (l-fluoro-l-methyl-ethyl) -l, 3,5-triazine-2 -yl] -N- (2-phenoxy-ethyl) amine, N- [4-amino-6- (l-fluoro-l-methyl-ethyl) -l, 3,5-triazin-2-yl] - N- [2- (3,5-difluorophenoxy) ethyl] amine, N- [4-amino-6- (l-fluoro-l-methyl-ethyl) -l, 3,5-triazine-2 -yl] -N- [2- (3,5-dimethyl-phenoxy) -ethyl] -amine for controlling undesirable plants in cotton, barley, maize, beet and wheat crops.

11. Herbicidal agent, characterized in that it contains a compound according to one of claims 1 to 4 and conventional extenders and / or surface-active agents.