WO2004077950A1

WO2004077950A1 - Substituted triazolecarboxamides

Info

Publication number: WO2004077950A1
Application number: PCT/EP2004/001746
Authority: WO
Inventors: Ernst Rudolf Gesing; Mark Wilhelm Drewes; Peter Dahmen; Dieter Feucht; Rolf Pontzen; Peter Lösel; Qinghong Tang; Jin Cao; Liang Chen; Xiuli Li; Yongbin Zhang; Xiaofei Li; Dinghui Zou; Honghuii Wu
Original assignee: Bayer Cropscience Ag
Priority date: 2003-03-06
Filing date: 2004-02-23
Publication date: 2004-09-16
Also published as: CN1526704A; AR043445A1

Abstract

The invention relates to substituted triazolecarboxamides of the Formula (I) in which R1, R2 and R3 are as defined in the description, to their use as crop treatment agents, in particular as herbicides, and to processes and intermediates 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 represents hydrogen, optionally substituted alkyl having 1 to 6 carbon atoms or optionally substituted dialkylamino having 1 to 6 carbon atoms in each alkyl group,

R² represents hydrogen or optionally substituted alkyl having 1 to 6 carbon atoms,

R³ represents a halogenoalkyl of the formula

wherein

the total number of carbon atoms is higher than 2,

R⁴ represents hydrogen, ethyl, n- or i-propyl or n-, s-, i- or t- butyl, and

R⁵ represents halogenoalkyl having 1 to 6 carbon atoms and 1 to 3 halogen 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-confϊgured) forms or diastereomeric forms. In these cases, the invention relates both to the use of the different possible individual enantiomeric or stereoisomeric forms of the compounds of the 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 preferably represents hydrogen, alkyl having 1 to 4 carbon atoms or dialkylamino having 1 to 4 carbon atoms in each alkyl group.

R¹ more preferably represents hydrogen, methyl, ethyl, n- or i- propyl, dimethylamino or diethylamino.

R¹ most preferably represents hydrogen or dimethylamino.

R² preferably represents hydrogen or alkyl having 1 to 4 carbon atoms.

R² more preferably represents hydrogen, methyl, ethyl, n- or i- propyl.

R² most preferably represents hydrogen or methyl.

R⁴ preferably represents hydrogen, ethyl or i-propyl.

R⁵ preferably represents halogen-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl having 1 to 3 halogen atoms.

R , 5 more preferably represents substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is mono-substituted by halogen.

The preferred halogen substituent of R⁵ is chlorine. Especially preferred group of the compounds of formula (I) are the groups where R³ represents 2- chloro-1 -ethyl-ethyl, l-(chloromethyl)-propyl, l-(chloromethyl)-2-methyl-propyl, 2-chloro- propyl, 3-chloro-propyl, 2,3-dichloro-propyl, 2,2-dimethyl-3-chloro-propyl, 3-chloro-butyl, 2- chloro-butyl, 5-chloro-pentyl, 6-chlorohexyl, 2-fluoro-l -ethyl-ethyl, l-(fluoromethyl)-propyl, 1- (fluoromethyl)-2-methyl-propyl, 2-fluoro-propyl, 3-fluoro-propyl, 2,3-fluoro-propyl, 2,2- dimethyl-3-fluoro-propyl, 3-fluoro-butyl, 2-fluoro-butyl, 5-fluoro-pentyl, 6-fluorohexyl, 2-bromo- 1 -ethyl-ethyl, l-(bromomethyl)-propyl, l-(bromomethyl)-2-methyl-propyl, 2-bromo-propyl, 3- bromo-propyl, 2,3-dibromo-propyl, 2,2-dimethyl-3 -bromo-propyl, 3-bromo-butyl, 2-bromo-butyl, 5-bromo-pentyl and 6-bromohexyl. In this group the compounds wherein the halogen atom is chlorine are especially emphazised.

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

The novel substituted triazolecarboxamides of the formula (I) are obtained when,

substituted triazolecarboxamides of the formula (I)'

in which

R¹ and R² are defined as above, and

R^3' represents a hydroxy-substituted alkyl of the formula

wherein

the total number of carbon atoms is higher than 2,

R⁴ represents hydrogen, ethyl, n- or i-propyl or n-, s-, i- or t- butyl, and

R⁶ represents hydroxy-substituted alkyl having 1 to 6 carbon atoms and 1 to 3 hydroxy substituents are reacted with a halogenating agent.

In formula (I)¹ R⁶ preferably represents hydroxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl having 1 to 3 hydroxy substituents or more preferably represents substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is mono-substituted by hydroxy.

As novel substances, the starting materials of the formula (I)' also form part of the subject-matter of the present application.

The compounds of the formula (I)' are obtained when

(a) amidines of the formula (II)

wherein R¹ and R² are defined as mentioned above

are reacted with oxalic acid amide hydrazides of the formula (III)

wherein R³ is defined as in formula (I)'

optionally in the presence of an reaction auxiliary and in the presence of an diluent or

(b) aminoguanidines of the formula (IN)

wherein R¹ and R² are defined as mentioned above,

are reacted with oxalic acid ester amides of the formula (V)

wherein R⁷ represents Alkyl and R³ is defined as in formula (I)'

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

The compounds of the formula (I)' are novel compounds which are also subject of this invention. In the formula (I)', R¹, R² and R ⁴ preferably, more preferably or most preferably have 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 or more preferred or most preferred for R¹, R² and R ⁴.

The formula (II) provides a general definition of the formamidines to be used as starting materials in the process (a) according to the invention for preparing compounds of the formula (I)\ In the formula (II), R¹ and R² preferably, more preferably or most preferably have 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 or more preferred or most preferred for R^] and R².

The starting materials of the formula (II) are known organic chemicals for synthesis and/or can be prepared by processes known per se.

The formula (III) provides a general definition of the oxalic acid amide hydrazides further to be used as starting materials in the process (a) according to the invention for preparing compounds of the formula (I)'. In the formula (III), R³ 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 R³.

The hydrazides of the formula (III) are known organic chemicals for synthesis and/or can be prepared by processes known in the art (cf. EP 0 412 358 Al, EP 0 126 326 A and example 2 below).

The formula (IN) provides a general definition of the aminoguanidines to be used as starting materials in the process (b) according to the invention for preparing compounds of the formula (I)'. In the formula (IN), R¹ and R² preferably, more preferably or most preferably have 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 R^nd R².

The aminoguanidines of the formula (IN) are known organic chemicals for synthesis and/or can be prepared by processes known in the art (cf. EP 0 332 991 Al).

The compounds of the formula (II) and (IN) can be used in form of acid adduct e.g. adducts with HC1 or acetic acid.

The formula (N) provides a general definition of the oxalic acid ester amides further to be used as starting materials in the process (b) according to the invention for preparing compounds of the formula (I)'. In the formula (N), R^3' 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 R³.

The starting materials of the formula (N) are known and/or can be prepared by processes known per se (cf. EP 0 332 991 Al).

The process according to the invention for preparing the compounds of the formula (I) is carried out using an halogenating agent. Suitable halogenating agents are the customary chemicals suitable for converting akylhydroxy groups to the corresponding halogenoalkyl groups. Examples of suitable halogenating agents which may be mentioned are: SOCl₂ or POCl₃.

Suitable reaction auxiliaries for the processes (a) and (b) 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, triethylamine, tripropyl- amine, tributylamine, ethyldiisopropylamine, Ν,Ν-dimethylcyclohexylamine, dicyclohexylamine,

^'• r 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-dimethylpyridine, 5-ethyl-

2-methylpyridine, 4-dimethylaminopyridine, N-methylpiperidine, l,4-diazabicyclo[2.2.2]octane

^• (DABCO), l,5-diazabicyclo[4.3.0]non-5-ene (DBN), or l,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

The process (a) according to the invention for preparing the compounds of the formula (I)' is preferably carried out using one or more diluents. Suitable diluents for carrying out the process (a) according to the invention arepreferably 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, di- isopropylether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether; ketones, such as acetone, butanone or methyl isobutyl ketone; nitriles, such as aceto- nitrile, propionitrile or butyronitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacet- amide, 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 mono- ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

The process (b) according to the invention for preparing compounds of the formula (I)'- is preferably carried out using a diluent. Suitable diluents are organic solvents which are customary for oxidation reactions. These preferably include chlorinated hydrocarbons, such as methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene, alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, iso- butanol and sec-butanol, carboxylic acids, such as formic acid, acetic acid and propionic acid.

When carrying out the processes (a) and (b) 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 processes are carried out at temperatures between +20°C and +150°C, preferably between 50°C and 100°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 starting materials are generally employed in approximately equimolar amounts, except for the halogenating agent which is usually used in molar excess. 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, Cirsiurn, 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, ycopersicon, 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 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.

Tackiiϊers 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 then; 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, ethal luralin, ethametsulfuron (-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop (-P-ethyl), fentrazamide, flamprop

(-isopropyl, -isopropyl-L, -methyl), flazasulfuron, florasulam, fluazifop (-P-butyl), fluazolate, flucarbazone (-sodium), fiufenacet, flufenpyr, flumetsulam, flumiclorac (-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone, fluoroglycofen (-ethyl), fiupoxam, 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 fungicides, 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 of the 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 of the 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 of the 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), IMI® (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 abovementioned 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:

Example 1

Step l

To a solution of 389 g (2,69 mol) of oxalic acid diethyl ester in 2000 ml methylene chloride there are dropped at -10°C 94.3 g (1.06 mol) 1-hydroxymethyl-propyl amine. The mixture is stirred for 1 hour at -10°C and for 12 hours at room temperature. The colourless precipitation is filtered off, washed with diethylether and air dried. This precipitation (41.5 g) is the corresponding oxalic acid diamide. The filtrate is concentrated under a reduced pressure of 1 mbar until the head temperature reaches 80°C. The red-brownish oily residue consists of mono amide which can be used without purification in the further steps.

This gives 105 g (53% of theory) of oxalic acid ethyl ester N-( 1-hydroxymethyl-propyl) amide.

Step 2

To a solution of 38.0 g (0,25 mol) of oxalic acid ethyl ester N-( 1-hydroxymethyl-propyl) amide in

200 ml ethanol there is dropped at room temperature a solution of 47.0 g (0,25 mol) 1-amino- 2,2,3-trimethylguadinium hydrochloride. Then 17.3 g (0,13 mol) potassium carbonate are added and the mixture is stirred for seven hours under reflux. Any solids are filtered off and the diluent is removed from the filtrate under reduced pressure. The oily residue is purified by chromatography using a silica gel solid phase and an ethanol/acetic acid ethyl ester (1 :2) mobil phase. The reaction product is obtained after washing with ether as a colourless solid. This gives 24 g (40% of theory) of 5-dimethylamino-4-methyl-4H-l,2,4-triazol-3-yl-carbonsaure- N-(l-hydroxymethyl-propyl) amide of melting point 86°C.

Step 3

Example 1

To 26 g (158 mmol) 5 -dimethylamino-4-methyl-4H-l,2,4-triazol-3-yl-carbonsaure-N-( 1-hydroxymethyl-propyl) amide there are added 100 ml SOCl₂ and the reaction mixture is heated for four hours under reflux. Any excess of SOCl₂ is removed under vacuum and to the residue there is added 200 ml methylene chloride. The obtained organic phase is washed with ice water,, saturated NaHC0₃ solution and another time with water. Then the organic phase is dried with sodium sulfate. The diluent is removed under vacuum and the remaining residue treated with petroleum ether, filtered and air dried. A colourless solid is obtained.

This gives 24 g (40% of theory) of 5-dimethylamino-4-methyl-4H-l,2,4-triazol-3-yl-carbonsaure- N-(l-chorornethyl-propyl) amide 158 - 160°C.

Example 2

Step l

To a solution of 22.13 g (150 mmol) of oxalic acid diethyl ester in 200 ml methylene chloride there are dropped at -20°C to -10°C a solution of 11.28 g (150mmol) 2-hydroxy-propyl amine in 20 ml methylene chloride. The mixture is stirred for 3 hours at -10°C. The colourless precipitation is filtered off washed with diethylether. This precipitation (77 g) is the corresponding oxalic acid diamide. The filtrate is concentrated to dryness upon heating and the remaining solid is purified by chromatography using a silica gel solid phase and an acetic acid ethyl ester/petroleum ether (1:2) obil phase. This gives 9.1 g (35% of theory) of oxalic acid ethyl ester N-(2-hydroxy-propyl) amide as a colourless oil (n_D ²⁰ 1.4512).

Step 2

To a solution of 7.0 g (40 mmol) oxalic acid ethyl ester N-(2-hydroxy-propyl) amide in 100 ml ethanol there is dropped 3.0 g (60 mmol) hydrazine monohydrate in 20 ml ethanol. The mixture is heated at 42°C for two hours and stirred for one hour at room temperature. The colourless precipitation is filtered off arid washed with ether.

This gives 5.3 g (82% of theory) of oxalic acid hydrazide N-(2-hydroxymethyl-propyl) amide of melting point 145°C.

Step 3

3.5 g (22 mmol) oxalic acid hydrazide N-(2-hydroxymethyl-propyl) amide and 2.71 g (26 mmol) of formamidine (as acetic acid monoadduct) are dissolved in 50 ml n-butanol at room temperature. The reaction product is isolated after cooling by filtration and washing of the solid residue with diethyl ether.

This gives 1.75 g (47% of theory) of 4H-l,2,4-triazol-3-yl-carbonsaure-N-(2-hydroxy-propyl) amide of melting point 193°C.

Step 4

Example 2

To 20 ml SOC-2 there is added in small portions 2.74 g (16 mmol) 4H-l,2,4-triazol-3-yl- carboxylic acid-N-(2-hydroxy-propyl) amide under stirring. Then the reaction mixture is heated under reflux for two hours before the excess SOCl₂ is removed under vacuum and the residue is crystalized from ether, filtered and air dried.

This gives 1.75 g (47% of theory) of 4H-l,2,4-triazol-3-yl-carbonsaure-N-(2-chloro-propyl) amide of melting point 106°C.

Example (D'-3

20 g (124 mmol) oxalic acid hydrazide N-(2-hydroxymethyl-propyl) amide, 11.74 g (124 mmol) acetamidine hydrochloride and 10 g (72 mmol) potassium carbonate are stirred in 50 ml n-butanol for one hour at room temperature. The reaction mixture is then heated for 12 hours under reflux. After cooling to room temperature the precipitation is filtered off and is then digested with water. The remaining solid residue is again filtered, washed with water and air dried.

This gives 5.52 g (23% of theory) of 5-methyl-4-methyl-4H-l,2,4-triazol-3-yl-carbonsaure-N-(2- ■ hydroxy-propyl) amide of melting point 179°C.

Analogously to Preparation Examples 1 and 2, and in accordance with the general description of the process according to the invention, it is also possible to prepare, for example, the compounds of the formula (I) listed in Table 1 below.

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

Analogously to Preparation Examples (I)'-l, -2 and -3 and in . accordance with the general description of the processes according to the invention, it is also possible to prepare, for example, the compounds of the formula (I)' listed in Table 2 below.

Table 2: Examples of compounds of the formula (I)'

Analogously to Preparation Examples (V)-l and (N)-2, and in accordance with the general description of the process according to the invention, it is also possible to prepare, for example, the compounds of the formula (V) listed in Table 3 below.

Table 3: Examples of compounds of the formula (N)

Analogously to Preparation Example (III)-l, and in accordance with the general description of the process according to the invention, it is also possible to prepare, for example, the compounds of the formula (III) listed in Table 4 below.

Table 4: Examples of compounds of the formula (III)

The LogP values given in the Tables were determined in accordance with EEC directive 79/831 Annex V.A 8 by HPLC (High Performance Liquid Chromatography) using a reversed-phase column (C 18). Temperature: 43°C.

Mobile phases for the determination in the acidic range: 0.1% aqueous phosphoric acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile - the corresponding data in Table 1 are labelled ^a).

Calibration was carried out using unbranched alkan-2-ones (with from 3 to 16 carbon atoms) whole logP values are known (determination of the logP values by the retention times using linear interpolation between two successive alkanones).

The lambda-max values were determined in the maxima of the chromatography signals, using the UV spectra from 200 nm to 400 nm.

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 of the untreated control.

The figures denote:

0% = no effect (like untreated control)

100% = total destruction

In this test, for example, the compounds of Preparation Examples 1 and 8 exhibit strong activity against weeds.

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 of the 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 1, 3 and 8 exhibit strong activity against weeds.

Table B

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

Example 3

Example 1

Example 8

Example C

Myzus test

Solvent: parts by weight of dimethylformamide

Emulsifier: 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.

Cabbage leaves (Brassica oleracea) which are heavily infested by aphids (Myzus persicae) are treated by being dipped into the preparation of the active compound of the 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 of the beetle larvae have been killed.

In this test, for example, the following compounds from the preparation examples show an activity against the insects:

Compounds of examples 2, 3, 5, 9, 10, 11, 12 and 13.

Table C Myzus-Test active ingredient concentration mortality in ppm in % nach 6^d

Example 2

Example 3

Example 5

Table C (continued) Myzus-Test active ingredient concentration mortality in ppm in % nach 6^d

Example 9

Example 10

Example 11

Tabelle C (continued) Myzus-Test active ingredient concentration mortality in ppm in % nach 6^d

Example 12

Example 13

Example D

Plutella test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 part by weight of alkylaryl polyglycolether

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of the active compound of the desired concentration and are infested with larvae of the diamond- black moth (Plutella xylostella) as long as the leaves are still moist.

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

Compound of example 14.

Table D Plutella-Test active ingredient concentration mortality in ppm in % nach 7^d

Example 14

Example E

Tetranychus test (OP-resistant/dip test)

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 part by weight of alkylaryl poly glycolether

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 of the 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 of the spider mites have been killed.

In this test, for example, the following compounds from the preparation examples show an activity against the mites:

Compounds of example 5, 7 and 11.

Table E Tetranychus-Test (OP-resistant/dip test ) active ingredient concentration mortality in ppm in % nach 7^d

Example 5

Example 7

Example 11

Example F

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.

In this test, for example, the following compounds from the preparation examples show an activity against the larvae:

Compound of example 2.

Table F Meloidogyne-Test active ingredient concentration mortality in ppm in % nach 14^d

Example 2

Claims

Patent claims

1. A compound of the formula (I)

in which

R³ represents a halogenoalkyl of the formula

wherein

the total number of carbon atoms is higher than 2,

R⁴ represents hydrogen, ethyl, n- or i-propyl or n-, s-, i- or t- butyl, and

2. A compound according to claim 1, wherein

R¹ represents hydrogen, alkyl having 1 to 4 carbon atoms or dialkylamino having 1 to 4 carbon atoms in each alkyl group,

R² represents hydrogen or alkyl having 1 to 4 carbon atoms, R⁴ represents hydrogen, ethyl or i-propyl, and

R⁵ represents halogen-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t- butyl having 1 to 3 halogen atoms.

3. A compound according to claim 1, wherein

R¹ hydrogen, methyl, ethyl, n- or i- propyl, dimethylamino or diethylamino,

R² represents hydrogen, methyl, ethyl, n- or i- propyl, and

R⁵ represents substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is mono-substituted by halogen.

4. A compound according to claim 1, wherein

R¹ hydrogen or dimethylamino, and

R² represents hydrogen or methyl.

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

substituted triazolecarboxamides of the formula (I)'

in which

R¹ and R² are defined as in claim 1, and

R^3' represents a hydroxy-substituted alkyl of the formula

wherein the total number of carbon atoms is higher than 2,

R⁴ represents hydrogen, ethyl, n- or i-propyl or n-, s-, i- or t- butyl, and

R⁶ represents hydroxy-substituted alkyl having 1 to 6 carbon atoms and 1 to 3 hydroxy substituents, .

are reacted with a halogenating agent.

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

7. A herbicidal composition, comprising a compound according to Claim 1 and customary extenders and/or surfactants.

8. Method for controlling unwanted vegetation, characterized in that at least one compound according to Claim 1 is allowed to act on the unwanted plants and/or their habitat.

9. A compound of the formula (I)'

wherein

R³ represents a hydroxy-substituted alkyl of the formula

wherein

the total number of carbon atoms is higher than 2,

R⁴ represents hydrogen, ethyl, n- or i-propyl or n-, s-, i- or t- butyl, and represents hydroxy-substituted alkyl having 1 to 6 carbon atoms and 1 to 3 hydroxy substituents.