WO2004101532A1

WO2004101532A1 - Substituted triazolecarboxamides

Info

Publication number: WO2004101532A1
Application number: PCT/EP2004/004705
Authority: WO
Inventors: Ernst R. F. Gesing; Mark Wilhelm Drewes; Peter Dahmen; Dieter Feucht; Rolf Pontzen; Peter Lösel; Karl-Heinz Kuck; Qinghong Tang; Jin Cao; Liang Chen; Xiuli Li; Yongbin Zhang; Xiaofei Li; Dinghui Zou; Honghui Wu; Christian Arnold; Christoph Erdelen
Original assignee: Bayer Cropscience Ag; Lubos-Erdelen, Angelika
Priority date: 2003-05-13
Filing date: 2004-05-04
Publication date: 2004-11-25
Also published as: CN1548425A

Abstract

Substituted triazolecarboxamides A b s t r a c t The invention relates to substituted triazolecarboxamides of the formula (I) in which R1, R2, R3 and R4 are as defined in the description, to their use as crop treatment agents, in particular as herbicides, and to processes for their preparation.

Description

Substituted triazolecarboxamides

The invention relates to novel substituted triazolecarboxamides, to a process for their preparation and to their use as crop treatment agents, in particular as herbicides.

It is already known that certain substituted, triazolecarboxamides have herbicidal properties (cf. EP 0 332 991 Al, EP 0 399 285 Al, EP 0 412 358 Al). However, the action of these compounds is not entirely satisfactory.

This invention now provides the substituted triazolecarboxamides of the formula (I)

in which

R¹, R² represent independently from another the same or a different alkyl group having 1 to 6 carbon atoms which is optionally substituted,

R³ represents optionally substituted alkyl having 1 to 6 carbon atoms,

R⁴ represents a group of the formula

wherein

n is 1, 2, 3, 4 or 5,

R⁵ represents halogen, Cι-C₈-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkmyl, Cι-C₈-alkoxy, C₂-C₈-alkenyloxy, C₃-C₈-alkinyloxy, C_rC₈-alkylthio, Cι-C₆-alkylsulfmyl, C C₆- alkylsulfonyl, C C₆-halogenalkyl, Cι-C₆-halogen-alkoxy, C₂-C₈-halogen- alkenyloxy, halogen- - -alkylthio, halogen-C C₄-all ylsulfinyl, halogen-C_rC₄- alkylsulfonyl, di-(Cι-C₄-alkyl)amino, hydroxy, nitro, cyano, amino, or CO-O-R¹, or represents in each case optionally halogen-, Cι-C₆-alkyl-, C C₆-alkoxy-, C C₆- alkthio-, di-(C C₄-alkyl)amino-, ^• Cι-C -kalogenalkyl-, Cι-C₄-halogenalkoxy-, nitro- or cyano-substituted C₃-C₆-cycloalkyl, piperidin-1-yl, phenyl, naphthyl, phenyl-C]-C₄-alkyl or phenoxy,

or R⁵ represents an unsaturated alkanediyl group forming a naphthyl group together with the phenyl to which it is bonded.

m is 0, 1, 2 or 3,

A represents

, and

R⁶ represents hydrogen or optionally substituted alkyl having 1 to 6 carbon atoms.

Alkyl is in each case straight-chain or branched as far as this is possible.

Optionally substituted radicals can be mono- or polysubstituted, and in the case of poly- substitution, the substituents can be identical or different. Possible substituents are for instance alkoxy having 1 to 4 carbon atoms or halogen.

Halogen stands for fluorine, chlorine, bromine or iodine and preferably for fluorine, chlorine or bromine. Compounds wherein the halogen atom is chlorine are especially preferred.

The compounds of the formula (I) according to the invention may contain one or more asymmetrically substituted carbon atoms, in which cases they may be present in different enantiomeric (R- and S-configured) forms or diastereomeric forms. In these cases, the mvention relates both to the use of the different possible individual enantiomeric or stereoisomeric forms of the compounds ofthe formula (I) and of mixtures of these isomeric compounds.

Preferred substituents or ranges of the radicals present in the formulae given above and below are defined below.

R¹, R² preferably represent alkyl having 1 to 4 carbon atoms.

R¹, R² more preferably represent methyl, ethyl, n- or i- propyl.

R¹, R² most preferably represent methyl.

R³ preferably represents alkyl having 1 to 4 carbon atoms.

R³ more preferably represents methyl, ethyl, n-^'or i-propyl. R³ most preferably represents methyl.

n preferably is 1, 2 or 3.

n more preferably is 1.

R⁵ preferably represents fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, tert.-butyl, methoxy, ethoxy, propoxy, isopropoxy, tert.-butoxy, allyloxy, 2-butenyloxy, methylthio, ethylthio, isopropylthio, propylthio, tert.-butylthio, methylsulfinyl, ethyl- sulfinyl, methylsulfonyl, ethylsulfonyl, trifluoromethyl, difluoromethoxy, ^' trifluoro- methoxy, difluoromethylthio, trifluoromethylthio, trifluoromethylsulfinyl, trifluoro- methylsulfonyl, dimethylamino, diethylamino, hydroxy, nitro, cyano, amino or CO-O-R¹, or represents in each case optionally fluorine-, chlorine-, bromine-, methyl-, ethyl-, isopropyl-, methoxy-, ethoxy-, isopropoxy-, tert.-butoxy-, methylthio-, ethylthio-, isopropylthio-, dimethylamino-, diethylamino-, ethyltrifluormethyl-, trifluoromethoxy-, nitro- or cyano-substituted cyclopentyl, cyclohexyl, piperidin-1-yl, phenyl or phenoxy,

R⁵ more preferably represents fluorine, chlorine, bromine, dimethylamino, nitro, or represents in each case optionally fluorine-, chlorine- or bromine- substituted methyl, ethyl, n- or i-propyl, tert.rbutyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, propylthio, isopropylthio or tert.-butylthio or represents CO-0-CH₃ or represents cyclopentyl, cyclohexyl, or represents optionally methyl substituted peperidin-1-yl, or represents optionally chlorine-, fluorine-, bromine-, methyl-, methoxy-, methylthio- or dimethylamino-substituted phenoxy

R⁵ most preferably represents fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, trifluoromethoxy.

R^δ preferably represents hydrogen, methyl, ethyl or isopropyl.

R^δ more preferably represents methyl.

m preferably is 0, 1 or 2. m more preferably is 0 or 1. ■

The group of compounds wherein m is 0 may be especially mentioned. Another specific group of compounds is that wherein R⁵ is fluorine, chlorine or bromine, m is 1 and R⁶ is methyl.

The novel substituted triazolecarboxamides ofthe formula (I) have strong herbicidal activity.

The compounds ofthe formula (I) are obtained when

aminoguanidines of the formula (II) or acid adducts thereof

wherein

R¹, R² and R³ are defined as mentioned above,

are reacted with oxalic acid ester amides ofthe formula (III)

wherein

R⁷ represents alkyl and R⁴ is defined as mentioned above,

optionally in the presence of a diluent and optionally in the presence of a reaction auxiliary.

R⁷ preferably represents Cr -alkyl and in particular ethyl.

The aminoguanidines of the formula (II) are known compounds or can be prepared according to processes known per se (cf. EP 0 332 991 Al). In the formula (II), R¹, R² and R³ preferably, more preferably or most preferably have those meanings which have already been mentioned above, in connection with the description ofthe compounds ofthe formula (I) according to the invention, as being preferred or more preferred or most preferred for R¹, R² and R³. The compounds of formula (II) can be used as such or in form of their adducts with inorganic or organic acids, preferably as HCl-adducts. The formula (III) provides a general definition of the oxalic acid ester amides further to be used as starting materials. In the formula (III), R⁴ preferably, more preferably or most preferably has those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred, more preferred or most preferred for R⁴.

The starting materials of the formula (III) are known and/or can be prepared by processes known per se (cf. EP 0 332 991 Al). The amines of the formula R⁴-NH needed for making the compounds of formula (III) are themselves known and/or can be prepared by processes known per se (cf. WO 97/08156; WO 98/15537)

Suitable reaction auxiliaries for preparing compounds of formula (I) according to the invention are, in general, the customary inorganic or organic bases or acid acceptors. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides, such as, for example, sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide, ethoxide, n- or isopropoxide, n-, iso-, s- or t-butoxide or potassium methoxide, ethoxide, n- or isopropoxide, n-, iso-, s- or t-butoxide; furthermore also basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamme, tripropylamine, tributylamine, ethyldiisopropyl- amine, N,N-dimethylcyclohexylamine, dicyclohexylamine, ethyldicyclohexylamine, N,N-di- methylaniline, N,N-dimethylbenzylamine, pyridine, 2-methyl-, 3 -methyl-, 4-methyl-, 2,4-di- methyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethylpyridine, 5-ethyl-2-methylpyridine, 4- dimethylaminopyridine, N-methylpiperidine, l,4-diazabicyclo[2.2.2]octane (DABCO), 1,5-diaza- bicyclo[4.3.0]non-5-ene (DBN), or l,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

The process for preparing the compounds of the formula (I) is preferably carried out using one or more diluents. Suitable diluents for carrying out the process according to the invention are preferably inert organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether; ketones, such as acetone, butanone or methyl isobutyl ketone; nitriles, such as acetonitrile, propionitrile or butyronitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; esters, such as methyl acetate or ethyl acetate; sulphoxides, such as dimethyl sulphoxide; alcohols, such as methanol, ethanol, n- or isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

When carrying out the processes according to the invention for preparing compounds of the formula (I), the reaction temperatures can be varied within a relatively wide range. In general, the process is carried out at temperatures between +30°C and +150°C, preferably between 50°C and 80°C.

The processes according to the invention are generally carried out under atmospheric pressure. However, it is also possible to carry out the processes according to the invention under elevated or reduced pressure - in general between 0.1 bar and 10 bar.

For carrying out the processes according to the invention, the 1.0 to 1.5 moles, preferably 1.0 to 1.2 moles oxalic ester amide and optionally 1.0 to 5.0 moles of the reaction auxiliary are employed per mole of the aminoguanidine or its acid adduct thereof employed in approximately equimolar amounts. However, it is also possible to use a relatively large excess of one of the components in other processes according to the invention. The reaction mixture is generally stirred at the required temperature for a number of hours. Work-up is carried out. by customary methods (cf. the Preparation examples).

The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weed killers. Weeds in the broadest sense are understood to mean all plants which grow in locations where they are undesired. 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 be used, for example, in connection with the following plants:

Dicotyledonous 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, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium. Dicotyledonous crops of the genera: Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia.

Monocotyledonous weeds of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.

Monocotyledonous crops of the genera: Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea.

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

The active compounds according to the invention are suitable, depending on the concentration, for the total control of weeds, for example on industrial terrain and rail tracks, and on paths and areas with and without tree plantings. Similarly, the active compounds according to the invention can be employed for controlling weeds in perennial crops, for example forests, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop fields, on lawns, turf and pastureland, and for the selective control of weeds in annual crops.

The compounds of the formula (I) according to the invention have strong herbicidal activity and a broad active spectrum when used on the soil and on above-ground parts of plants. To a certain extent they are also suitable for the selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous crops, both by the pre-emergence and by the post-emergence method.

At certain concentrations or application rates, the active compounds according to the invention can also be employed for controlling animal pests and fungal or bacterial plant diseases. Preferably they can be used as fungicides, insecticides and nematicides. If appropriate, they can also be used as intermediates or precursors for the synthesis of other active compounds.

All plants and plant parts can be treated in accordance with the invention. Plants are to be understood as meaning in the present context all plants and plant populations such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional plant breeding and optimization methods or by biotechnological and recombinant methods or by combinations of these methods, including the transgenic plants and inclusive of the cultivars protectable or not protectable by plant breeders' rights. Plant parts are to be understood as meaning all parts and organs of plants above and below the ground, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes. The plant parts also include harvested material, and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offsets and seeds.

Treatment according to the invention of the plants and plant parts with the active compounds is carried out directly or by allowing the compounds to act on their surroundings, environment or storage space by the customary treatment methods, for example by immersion, spraying, evaporation, fogging, scattering, painting on and, in the case of propagation material, in particular in the case of seeds, also by applying one or more coats.

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, natural and synthetic materials impregnated with active compound, and microencapsulations in polymeric materials.

These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is, liquid solvents and/or solid carriers, optionally with the use of surfactants, that is, emulsifiers and/or dispersants, and/or foam formers.

If the extender used is water, it is also possible, for example, to use organic solvents as cosolvents. The following are essentially suitable as liquid solvents: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chloro- benzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example mineral oil 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 sulphoxide, or else water.

Suitable solid carriers are: for example ammonium salts and ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic materials such as highly-disperse silica, alumina and silicates; suitable solid carriers for

^■granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, or else protein hydrolysates; suitable dispersants are: for example lignosulphite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other possible additives are mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic colorants such alizarin colorants, azo colorants and metal phthalocyanine colorants, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

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

For controlling weeds, the active compounds according to the invention, as such or in their formulations, can also be used as mixtures with known herbicides and/or substances which improve the compatibility with crop plants ("safeners"), finished formulations or tank mixes being possible. Also possible are mixtures with weed-killers comprising one or more known herbicides and a safener.

Possible components for the mixtures are known herbicides, for example

acetochlor, acifluorfen (-sodium), aclonifen, alachlor, alloxydim (-sodium), ametryne, amicarbazone, amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafenidin, azimsulfuron, beflubutamid, benazolin (-ethyl), benfuresate, bensulfuron (-methyl), bentazone, benzfendizone, benzobicyclon, benzofenap, benzoylprop (-ethyl), bialaphos, bifenox, bispyribac (-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butafenacil (-allyl), butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentrazone (-ethyl), chlomethoxyfen, chloramben, chloridazon, chlorimuron (-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinidon (-ethyl), cinmethylin, cinosulfuron, clefoxydim, clethodim, clodinafop (-propargyl), clomazone, clomeprop, clopyralid, clopyrasulfuron (-methyl), cloransulam (-methyl), cumyluron, cyanazine, cybutryne, cycloate, cyclosulfamuron, cycloxydim, cyhalofop (-butyl), 2,4-D, 2,4-DB, desmedipham, diallate, dicamba, dichlorprop (-P), diclofop (-methyl), diclosulam, diethatyl (-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, epropodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron (-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop (-P-ethyl), fentrazamide, flamprop (-isopropyl, -isopropyl-L, -methyl), flazasulfuron, florasulam, fluazifop (-P -butyl), fluazolate, flucarbazone (-sodium), flufenacet, flufenpyr, flumetsulam, fiumiclorac (-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone, fluoroglycofen (-ethyl), flupoxam, flupropacil, flurpyrsulfuron (-methyl, -sodium), flurenol (-butyl), fluridone, fluroxypyr (-butoxypropyl, -meptyl), 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, imazosulfuron, iodosulfuron (-methyl, -sodium), ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, ketospiradox, lactofen, lenacil, linuron, MCPA, mecoprop, mefenacet, mesotrione, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (alpha-) metolachlor, metosulam, metoxuron, metribuzin, metsulfuron (-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pendralin, penoxysulam, pentoxazone, pethoxamid, phenmedipham, picolinafen, piperophos, pretilachlor, primisulfuron (-methyl), profluazol, profoxydim, prometryn, propachlor, propanil, propaquizafop, propisochlor, propoxycarbazone (-sodium), propyzamide, prosulfocarb, prosulfuron, pyraflufen (-ethyl), pyrazogyl, pyrazolate, pyrazosulfuron (-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyridatol, pyriftalid, pyriminobac (-methyl), pyrithiobac (-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop (-P-ethyl, -P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron ^'(-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron (-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron (-methyl), triclopyr, tridiphane, trifluralin, trifloxysulfuron, triflusulfuron (-methyl), tritosulfuron.

Furthermore suitable for the mixtures are known safeners, for example AD-67, BAS-145138, ben- oxacor, cloquintocet (-mexyl), cyometrinil, 2,4-D, DKA-24, dichlormid, dymron, fenclorim, fen- chlorazol (-ethyl), flurazole, fluxofenim, furilazole, isoxadifen (-ethyl), MCPA, mecoprop (-P), mefenpyr (-diethyl), MG-191, oxabetrinil, PPG- 1292, R-29148. A mixture with other known active compounds, such as ftmgicides, insecticides, acaricides, nematicides, bird repellents, 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 a customary manner, for example by watering, spraying, atomizing or broadcasting.

The active compounds according to the invention can be applied both before and after emergence ofthe plants. They can also be incorporated into the soil before sowing.

The amount of active compound used can vary within a relatively wide range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.

As already mentioned above, it is possible to treat all plants and their parts according to the invention. In a preferred embodiment, wild plant species and cultivars, or those obtained by conventional biological breeding, such as crossing or protoplast fusion, and parts thereof, are treated. In a further preferred embodiment, transgenic plants and cultivars obtained by genetic engineering, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated. The term "parts" or "parts of plants" or "plant parts" has been explained above.

Particularly preferably, plants of the cultivars which are in each case commercially available or in use are treated according to the invention. Cultivars are to be understood as meaning plants having certain properties ("traits") and which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They can be varieties, bio- or genotypes.

Depending on the plant species or cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive ("synergistic") effects. Thus, for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the substances and compositions which can be used according to the invention also in combination with other agrochemically active compounds, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought, or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products are possible which exceed the effects which were actually to be expected.

The transgenic plants or cultivars (i.e. those obtained by genetic engineering) which are preferably treated according to the invention include all plants which, in the genetic modification, received genetic material which imparted particularly advantageous useful properties ("traits") to these plants. Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products. Further and particularly emphasized examples of such properties are a better defence of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and or viruses, and also increased tolerance ofthe plants to certain herbicidally active compounds. Examples of transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), maize, soya beans, potatoes, cotton, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), and particular emphasis is given to maize, soya beans, potatoes, cotton and oilseed rape. Traits that are emphasized are in particular increased defence ofthe plants against insects by toxins formed in the plants, in particular those formed in the plants by the genetic material from Bacillus thuringiensis (for example by the genes CryΙA(a), CryIA(b), CryΙA(c), CryllA, CrylllA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CrylF and also combinations thereof) (hereinbelow referred to as "Bt plants"). Traits that are also particularly emphasized are the increased defence of the plants to fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits that are furthermore particularly emphasized are the increased tolerance, of the plants to certain herbicidally active compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphinotricin (for example the "PAT" gene). The genes which impart the desired traits in question can also be present in combination with one another in the transgenic plants. Examples of "Bt plants" which may be mentioned are maize varieties, cotton varieties, soya bean varieties and potato varieties which are sold under the trade names YIELD GARD® (for example maize, cotton, soya beans), KnockOut® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants which may be mentioned are maize varieties, cotton varieties and soya bean varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosate, for example maize, cotton, soya bean), Liberty Link® (tolerance to phosphinotricin, for example oilseed rape), MI® (tolerance to imidazolinones) and STS® (tolerance to sulphonylurea, for example maize). Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance) which may be mentioned include the varieties sold under the name Clearfield® (for example maize). Of course, these statements also apply to cultivars having these genetic traits or genetic traits still to be developed, which plants will be developed and/or marketed in the future.

The plants listed can be treated according to the invention in a particularly advantageous manner with the compounds of the formula (I) or the active compound mixtures according to the invention where in addition to the effective control of the weeds, the above-mentioned synergistic effects with the transgenic plants or plant cultivators occur. The preferred ranges stated above for the active compounds or mixtures also apply to the treatment of these plants. Particular emphasis is given to the treatment of plants with the compounds or mixtures specifically mentioned in the present text.

The preparation and the use of the active compounds according to the invention is illustrated by the examples below.

Preparation Examples

Preparation of Example 55

Step l

2-(2-aminoethyl)-l-phenoxy-benzene (3.0g, 0.014 mol) in 5 ml CH₂C1₂ was added dropwise to a stirred solution of diethyl oxalate (4.1 g, 0.028 mol) in 10 ml CH₂C1₂ at 0°C. Stirring was continued overnight at room temperature. The CH₂C1₂ was evaporated and the excess diethyl oxalate was distilled in vacuo. 4.7 g of a residue were obtained. 1.2 g of the intermediate were purified by column chromatography (PE:EE = 2:1) to yield 0.9 g (75%) of oxalic acid ethyl ester N-[2-(2-phenoxoxy-phenyl)-ethyl] amide of a melting point of 51.7-52.4°C

Step 2

A mixture of l-amino-2,2,3-trimethylguanidinium hydrochloride (2.0 g, 0.013 mol), oxalic acid ethyl ester N-[2-(2-phenoxoxy-phenyl)-ethyl] amide (4.0 g, 0.013 mol), potassium carbonate (anhydrous; 1.8 g, 0.013 mol) in 40ml ethyl alcohol (absolute) was stirred at room temperature for 30 minutes, then refluxed for 16 h, and the residue was removed by filtration. The filtrate was concentrated by evaporation in vacuo and purified by column chromatography (EE) to yield 1.2 g (25%) of 5-dimethylamino-4-methyl-4H-l,2,4-triazol-3-yl-carbonic acid-N-[2-(2-phenoxoxy- phenyl)-ethyl] amide of melting point 132.0-132.8°C. Preparation of Example 4

Step l

Ethyl oxalyl chloride (5 g, 0.037 mol) in 10 ml CH₂C1₂ was added dropwise to a solution of 2- isopropyl-aniline (4.37 g, 0.032 mol) and triethylamine (3.71 g, 0.037 mol) in 25 ml CH₂C1₂ at 0°C with stirring. The mixture was stirred at room temperature overnight and washed with 2N HCl, saturated NaHC0₃ and brine, and then the organic phase was dried over anhydrous Na₂S0₄.

The solvent was evaporated and 6.5 lg of oxalic acid ethyl ester 2-isopropyl-anilide as a light brown oil were obtained (yield of 85.8%).

Step 2

A mixture of l-amino-2,2,3-trimethylguanidinium hydrochloride (2.34 g, 0.015 mol), oxalic acid ethyl ester N-(2-isopropyl-phenyl) amide (3.6 g, 0.015 mol), anhydrous K₂C0₃ (1.05 g, 0.008 mol) in 40 ml ethyl alcohol (absolute) was stirred at room temperature for 30 minutes, then refluxed for 16 h. After filtration, the filtrate was concentrated by evaporation in vacuo and the residue was purified by column chromatography (EE:PE=1:2) to yield 0.5 g 5-dimethylamino-4-methyl-4H- l,2,4-triazol-3-yl-carbonic acid 2-isopropyl-anilide as a light yellow oil (yield of 11.4% ).

Analogously to the Preparation Examples and in accordance with the general description of the process according to the invention, the compounds of the formula (I) listed in Table 1 below have been obtained.

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

Analogously to Preparation Examples and in accordance with the general description of the processes according to the invention, the compounds of the formula (III) listed in Table 2 below have been prepared.

Table 2: Examples of compounds ofthe formula (III)

Use examples

Example A

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 of a height of 5 - 15 cm are sprayed with the preparation of active compound such that the particular amounts of active compound desired are applied per unit area. The concentration of the spray liquor is chosen such that the particular amounts of active compound desired are applied in 1000 1 of water/ha.

After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development ofthe untreated control.

The figures denote:

0% = no effect (like untreated control)

100% = total destruction

In this test, for example, the compounds of Preparation Examples 2, 4, 5, 7, 8, 10, 11, 12, 13, 15, 16, 17, 30 and 33 exhibit strong activity against weeds, and in same cases also a good selectivity for the crops, such as corn. Table A-l

post-emergence / greenhouse g ai/ha corn Setaria Abutilon Amaranthus Ipomoea Sinapis

Example 5

Example 15

Table A-2 post-emergence / greenhouse g ai/ha Avena fatua Setaria Abutilon Amaranthus Ipomoea Sinapis

Example 2

1000 100 100 100 100 100 100

Example 4

Example 8

Table A-2 (continued) post-emergence / greenhouse g ai/ha Avena fatua Setaria Abutilon Amaranthus Ipomoea Sinapis

1000 100 100 100 100 100 100

Example 12

1000 90 100 100 100 100 100

Example 13

Table A-3

Example 17

Table A-4

post-emergence / greenhouse g ai/ha Setaria Abutilon Amaranthus Ipomoea Sinapis

Example 11, S-Isomeres

Example 16

Example 30

Example 33

Example B

Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

Seeds of the test plants are sown in normal soil. After 24 hours, the soil is sprayed with the preparation of active compounds such that the particular amount of active compound desired is applied per unit area. The concentration of active compound in the spray liquor is chosen such that the particular amount of active compound desired is applied in 1000 litres of water per hectare.

After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development ofthe untreated control. The figures denote:

0% = no effect (like untreated control)

100% = total destruction

In this test, for example, the compounds of the Preparation Examples 2, 4, 7, 8, 10, 12, exhibit strong activity against weeds, and in same cases also a good selectivity for the crops, such as corn.

Table B-l pre-emergence greenhouse g ai/ha Avena fatua Setaria Abutilon Amaranthus Ipomoea

Example 2

Table B-2 pre-emergence / greenhouse g ai/ha corn Setaria Amaranthus Ipomoea Sinapis

Example 10, R-Isomeres

Table B-3 pre-emergence / Gewachshaus g ai/ha corn Setaria Abutilon Amaranthus Sinapis

Example 12

Table B-4 pre-emergence / greenhouse g ai/ha corn Poa Abutilon Datura Ipomoea Solanum

Example 4

Table B-5 pre-emergence / greenhouse g ai/ha Setaria Abutilon Amaranthus Ipomoea Sinapis

Example 7

Example 8

Example C

In vitro test for determining ED₅₀- values for microorganisms

A solution of the active ingredient in methanol is filled into the cavities of micro titer plates after having added the emulsifier PS 16. After evaporation of the solvent 200 μl of a potato-dextrose- medium is added in each cavity. The medium had been treated with a suitable concentration of spores or mycels respectively ofthe test fungi.

The resulting concentrations of the active ingredient are 0.1, 1, 10, and 100 ppm. The resulting concentration ofthe emulsifier is 300 ppm.

The micro titer plates are then incubated for 3-5 days on a shaker at a temperature of 22°C until an untreated control does show sufficient growth.

The evaluation is done photometrically at a wavelength of 620nm. From the measured values of the different concentrations a dose of the active ingredient is determined (ED₅₀ value) at which the growth ofthe fungi is reduced by 50% compared to the untreated control.

In this test the compounds according to examples 8, 9, 15, and 26 show ED₅₀ values of less then 0.1 for the microorganism pyricularia oryzae.

Table C

In vitro-test for determination of ED₅0- values of microorganism

Example 8 Pyricularia oryzae < 0,1

Example 9 Pyricularia oryzae < 0,1

Example 15 Pyricularia oryzae < 0,1

Example 26 Pyricularia oryzae < 0,1

Example D

Aphis gossypii test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 part by weight of alkylaryl polyglycolether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.

Leafs of cotton plants (Gossypium hirsutuum), which are heavily infected by green fly (aphis gossypii), are dipped into the preparation ofthe active compound ofthe desired concentration.

After the specified period of time, mortality in % is determined. 100 % means that all the green flies have been killed; 0 % means that none ofthe green flies have been killed.

In this test, for example, the following compounds from the preparation examples show a good activity:

Compounds of examples 23 and 27.

Table D

Aphis gossypii-Test

Active ingredient concentration Mortality in ppm in % nach 6^d

Example 23

Example 27

Example E

Meloidogyne test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 part by weight of alkylaryl polyglycolether

Vessels are filled with sand, a solution of the active ingredient, a suspension containing eggs and larvae of Meloidogyne incognita and salad seeds. The salad seeds germinate and the seedlings grow. Galls develop in the roots.

After the specified period the nematicidal activity is determined on the basis of the percentage of gall formation. 100 % means that no galls were found; 0 % means that the number of galls found on the roots of treated plants was equal to that in untreated control plants.

Compounds of examples 2, 16, 38, 39, 40, 42, 43, 44, and 45.

Table E

Meloidogyne-Test

Active ingredient concentration Mortality in ppm in%nachl4^d

Example 2

Example 38

Example 16

Example 39

Table E (continued) Meloidogyne-Test

Active ingredient concentration Mortality in ppm in % nach 14^d

Example 40

Example 42

Example 43

Example 44

Example 45

Example F

Myzus test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 part by weight of alkylaryl polyglycolether

Cabbage leaves (Brassica oleracea) which are heavily infested by aphids (Myzus persicae) are treated by being dipped into the preparation ofthe active compound ofthe desired concentration.

After the specified period of time, mortality in % is determined. 100 % means that all the beetle larvae have been killed; 0 % means that none ofthe beetle larvae have been killed.

Compounds of examples 3 and 6.

Table F

Myzus-Test

Active ingredient concentration Mortality in ppm in % nach 6^d

Example 3

Example 6

Example G

Myzus test (spraying application)

Solvent: 78 parts by weight of acetone

1.5 parts by weight dimethyl formamide

Emulsifier: 0,5 parts by weight of alkylaryl poly glycolether

Slices of cabbage leafs (Brassica chinensis), which are infected by aphis (Myzus Persicae) are sprayed with the preparation ofthe active compound.

After the specified period of time, mortality in % is determined. 100 % means that all the aphis have been killed; 0 % means that none ofthe aphis have been killed.

Compound of example 42.

Table G

Myzus-Test

Active ingredient concentration Mortality in ppm in % nach 4^d

Example 42

Example H

Spodoptera frugiperda test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 part by weight of alkylaryl polyglycolether

Cabbage leaves (Brassica oleracea) are dipped into the prepareation of the active compound of the desired concentration. Then caterpillars of Spodoptera frugiperda are placed on these leafs as long when they are still wet.

After the specified period of time, mortality in % is determined. 100 % means that all the caterpillars have been killed; 0 % means that none ofthe caterpillars have been killed.

Compounds of examples 9 and 12.

Table H

Spodoptera frugiperda -Test

Active ingredient concentration Mortality in ppm in % nach 7^d

Example 9

Example 12

Example I

Tetranychus test (OP-resistant dip test)

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 part by weight of alkylaryl polyglycolether

Bean plants (Phaseolus vulgaris) which are heavily infested with all stages of the two-spotted spider mite (Tetranychus urticae) are treated by being dipped into the preparation of the active compound ofthe desired concentration.

After the specified period of time, mortality in % is determined. 100 % means that all the spider mites have been killed; 0 % means that none ofthe spider mites have been killed.

In this test, for example, the following compounds from the preparation examples show a. good activity:

Compound of example 2.

Table I

Tetranychus-Test (OP-resistant/dip test)

Active ingredient concentration Mortality in ppm in % nach 7^d

Example 2

Claims

Patent claims

1. A compound ofthe formula (I)

in which

R³ represents optionally substituted alkyl having 1 to 6 carbon atoms,

R⁴ represents a group ofthe formula

wherein

n is 1, 2, 3, 4 or 5,

R⁵ represents halogen, Cι-C₈-aJkyl, C₂-C₈-alkenyl, C₂-C₈-alkinyl, -Cs-alkoxy,

C₂-C₈-alkenyloxy, C₃-C₈-alkinyloxy, Cι-C₈-alkylthio, Cι-C₆-alkylsulfinyl,

Cι-C₆-alkylsulfonyl, C C₆-halogenalkyl, C C₆-halogen-alkoxy, C₂-C₈- halogenalkenyloxy, halogen-C C₄-alkylthio, halogen-Cι-C₄-alkylsulfinyl, halogen-Cι-C -alkylsulfonyl, di-(C₁-C₄-alkyl)amino, hydroxy, nitro,

cyano, amino, or CO-O-R¹, or represents in each case optionally halogen-, Ci-Cβ-alkyl-, Cι-C₆-alkoxy-, Cι-C₆-alkthio-, di-(C_rC₄-alkyl)amino-, C C₄- kalogenalkyl-, Cι-C -halogenalkoxy-, nitro- or cyano-substituted C₃-C₆- cycloalkyl, piperidin-1-yl, phenyl, naphthyl, phenyl- -C₄-alkyl or phenoxy,

m is 0, 1, 2 or 3, R⁶ I

A represents /H\ , and

2. A compounds according to formula (I) of claim 1 wherein

R¹, R² represent alkyl having 1 to 4 carbon atoms,

R³ represents alkyl having 1 to 4 carbon atoms,

n is 1, 2 or 3,

R⁵ represents fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, tert.-butyl, methoxy, ethoxy, propoxy, isopropoxy, tert.-butoxy, allyloxy, 2-butenyloxy, rnethyl- thio, ethylthio, isopropylthio, propylthio tert.-butylthio, methylsulfmyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylthio, trifluoromethylthio, trifluoromemylsulfinyl, trifluoromethyl- sulfonyl, dimemylamino, die ylamino, hydroxy, nitro, cyano, amino, or CO-O-R¹, or represents in each case optionally fluorine-, chlorine-, bromine-, methyl-, ethyl-, isopropyl-, methoxy-, ethoxy-, isopropoxy-, tert.-butoxy-, methylthio-, ethylthio-, isopropylthio-, dimethylamino-, diethylamino-, ethyltrifiuormethyl-, trifluoromethoxy-, nitro- or cyano- substituted cyclopentyl, cyclohexyl, piperidin-1-yl, phenyl or phenoxy,

or R⁵ represents an unsaturated alkanediyl group forming a naphthyl group together with the phenyl to which it is bonded,

m is 0, 1 or 2, and

R⁶ represents hydrogen, methyl, ethyl or isopropyl.

3. A compound according to claim 2, wherein

R¹, R² represent methyl, ethyl, n- or i- propyl,

R³ represents methyl, ethyl, n- or i- propyl,

R⁵ represents fluorine, chlorine, bromine, dimethylamino, nitro, or represents in each case optionally fluorine-, chlorine- or bromine- substituted methyl, ethyl, n- or i- propyl, tert.-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, propylthio, isopropylthio or tert.-butylthio or represents CO-0-CH₃ or represents cyclopentyl, cyclohexyl, or represents optionally methyl substituted peperidin-1- yl, or represents optionally chlorine-, fluorine-, bromine-, methyl-, methoxy-, methylthio- or dimethylamino-substituted phenoxy

or R⁵ represents an unsaturated alkanediyl group forming a naphthyl group together with the phenyl to which it is bonded, and

R⁶ represents methyl.

4. A compound according to claim 3, wherein

R¹ , R² represent methyl,

R³ represents methyl, and

n is 1,

R⁵ represents fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, trifluoromethoxy, and

m is 0 or 1.

5. A process for preparing the compounds of formula (I) according to claim 1, characterized in that

aminoguanidines ofthe formula (II) or acid adducts thereof

wherein

R¹, R² and R³ are defined as mentioned above,

are reacted with oxalic acid ester amides ofthe formula (III)

wherein

R⁷ represents alkyl and

R⁴ is defined as mentioned above,

6. Use of a compound according to Claim 1 for controlling unwanted plants.

7. Use of a compound according to claim 1 to combat animal pests.

8. Use of a compound according to claim 1 to control fungal or bacterial plant diseases.

9. A herbicidal, pesticidal or fungicidal composition, comprising a compound according to

Claim 1 and customary extenders and/or surfactants.

10. A method for controlling unwanted vegetation and/or combating animal pests and/or fungi, characterized in that at least one compound according to Claim 1 is allowed to act on the unwanted plants and/or their habitat.