MXPA06009570A - Fungicidal mixtures - Google Patents

Abstract

The invention relates to fungicidal mixtures, containing the following in a synergistically effective quantity as active components:1) the triazolopyrimidine derivative of formula (I);and 2) a phenylamidine derivative of formula (II), in which the variables are defined as follows:R1, R4, R5 represent alkyl, alkenyl or alkynyl;R2, R3 represent cyano, alkyl, alkenyl, alkynyl, alkoxy, alkoxyalkyl, benzyloxy or alkylcarbonyl;m represents 0 or 1;A represents a direct bond, -O-, -S-, NRd, CHRe or -O-CHRe;R6 represents phenyl or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle, containing between one and four heteroatoms from the group comprising O, N or S, whereby the groups can be substituted according to the description. The invention also relates to a method for controlling pathogenic fungi using mixtures of compounds (I) and (II), to the use of compounds (I) and (II) for producing mixtures of this type and to agents that contain said mixtures.

Description

FUNGICIDE MIXES Description The present invention relates to fungicidal mixtures, which contain as active components 1) the triazolopyrimidine derivative of the formula I, 2) a phenylamidine derivative of the formula II, in which the variables have the following meanings: R1 is hydrogen, C8-C8-alkyl, C2-C8-alkenyl or C2-C8-alkynyl, which do not carry substituents or can be substituted by one to three Ra groups: R a is halogen, C C 8 -alkoxy, C-β-C 8 -haloalkoxy, C C 8 -alkylthio or phenyl, which may be substituted by halogen, CrC 8 -alkyl, C C 8 -halogenoalkyl, CrC 8 -alkoxy, C C 8 -haloalkoxy CrC8-alkylthio; R2, R3 can be the same or different radicals and represent hydrogen, cyano, C?-C8-alkyl, C2-C8-alkenyl, C2-C3-alkynyl, CrC8-alkoxy, C8-C8-alkoxyalkyl, benzyloxy or CrC8-alkylcarbonyl, which do not carry substituents or can be substituted by one to three Ra groups; R4 is hydrogen, Ci-C-β-alkyl, C2-C8-alkenyl or C2-C8-alkynyl, which do not carry substituents or can be substituted by one to three Rb groups: Rb is one of the groups mentioned for Ra, cyano, C (= O) Rc, C (= S) RC or S (O) pRc, Rc is C ^ Cs-alkyl, C? -C8-haloalkyl, CrC8-alkoxy, C? -8-haloalkoxy, CrC-alkylthio, amino, C-C8-alkylamino, di (C-C8-alkyl) amino or phenyl, which may be substituted by halogen, C, -C 8 -alkyl, C C 8 -haloalkyl, CrC 8 -alkoxy, C C 8 -haloalkoxy or C C 8 -alkylthio; m is 0 or 1; R5 is one of the groups mentioned for R4; A is a direct bond, -O-, -S-, NRa, CHRe or -O-CHRe; Rd, Re represent one of the groups mentioned for Ra; R6 is phenyl or a saturated, partially unsaturated or aromatic heterocyclic of five or six members, containing one to four heteroatoms of the group O, N or S, whose R6 groups do not bear substituents or can be substituted by one to three Rf groups: Rf is one of the groups mentioned for Rb or amino, d-Cβ-alkylamino, di (C?-C8-alkylamino), C- | -C8-halo-alkyl, C? -8-alkoxyalkyl, C2 -C8-alkenyloxyalkyl, C2-C8-alkynyloxyalkyl, Cs-alkylcarbonyloxy-Ci-Cs-alkyl, cyanoxy-C8-alkyl, C3-C6-cycloalkyl or phenoxy, the cyclic groups being able to be substituted by halogen, CrC8- alkyl, C Cs-haloalkyl, C? -C8-alkoxy, C?-C8-haloalkoxy or Cs-alkylthio; in a synergistically effective amount.

Furthermore, the invention relates to a method for combating harmful fungi with mixtures of compound I with compound II, the use of compound I with compound II for obtaining such mixtures, as well as products containing these mixtures.

The compound I, 4-methyl-piperidin-1-yl) -6- (2,4,6-trifluoro-phenyl) - [1, 2,4] triazolo [1, 5-ajpyrimidine, its preparation and its effect against Harmful fungi are known from the literature (WO 98/46607).

The compounds II, their preparation and their effect against harmful fungi are also known from the literature t (WO 00/46184).

Mixtures of triazolopyrimidines with other active ingredients are generally known from EP-A 988 790 and US 6 268 371.

Mixtures of the compounds II with other active ingredients are known from WO 03/024219.

In order to reduce the amounts of application and to broaden the spectrum of effect of the known compounds, the present invention aims to provide mixtures, which with a lower total amount of active principles applied have a better effect against harmful fungi (synergistic mixtures).

Therefore, the mixtures defined above were found. Furthermore, it has been found that when compound I and compound II are simultaneously applied together or separately, or when compound I and compound 11 are applied in succession, it is better to combat harmful fungi than with the individual compounds.

The mixtures of compound 1 with the active principle II or the joint or separate use of a compound I with the active principle II stand out for producing an excellent effect against a broad spectrum of phytopathogenic fungi, especially of the class of the ascomycetes, Basidiomycetes, Deuteromycetes, Oomycetes and Basidiomycetes. In part, the mixtures are systemically active, so they can be used in phytosanitation as disinfectants, foliar and soil fungicides.

They are especially important for combating a myriad of fungi in different crop plants, such as bananas, cotton, leguminous plants (eg cucumbers, beans, tomatoes and cucurbits), barley, grass, oats, coffee, potatoes, corn, fruits , rice, rye, soy, tomatoes, wine, wheat, ornamental plants, sugar cane, as well as countless seeds.

They are especially suitable for combating the following phytopathogenic fungi: Blumeria graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in vine, Puccinia species in cereals, Rhizoctonia species in cotton, rice, and turf, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis cinerea in strawberries, vegetables, ornamental plants and vine, Mycosphaerella species in bananas , peanuts and cereals, Pseudocercosporella herpotrichoides in wheat and barley, Phakopsora pachyrhizi and P. meibomiae in soybeans, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Pseudoperonospora species in cucurbits and hops, Plasmopara viticola in vine, Alternate species in legumes and fruits, as well as Fusarium and Verticillium species.

In addition, they can be used in the protection of materials (eg wood), for example against Paecilomyces variotii.

The compound I and the compounds II can be applied simultaneously together or separately, or successively, the order in which they are applied being unimportant for the effect of the treatment in the separate application.

The definitions of the variables indicated in formula 11 are collective terms generally representative for the following substituents: halogen: fluorine, chlorine, bromine and iodine; alkyl: saturated, linear or branched hydrocarbon radicals with 1 to 4, 6, 8 or 10 carbon atoms, eg CrC6-alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl , 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-di-methylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl , 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3 -dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl; haloalkyl: linear or branched alkyl groups with 1 to 2, 4 or 6 carbon atoms (as mentioned above), the hydrogen atoms in these groups being partially or completely substituted by halogen atoms such as those mentioned above: C2-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl or 1, 1 1-trifluoroprop-2-yl; alkenyl: saturated, linear or branched hydrocarbon radicals having 2 to 4, 6, 8 or 10 carbon atoms and one or two double bonds in arbitrary position, eg C2-C6-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl- 2-propenyl, 1-pentynyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2- butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, 1-dimethyl-2- propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1 -pentenyl, 2-methyl-1 -pentenyl, 3-methyl-1 -pentenyl, 4-methyl-1 -pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, -methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, 1 -dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3 -dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimetiH-butenyl, 2,3-dimethyl -2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl , 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, 1, 2-trimethyl-2-propenyl, 1-ethyl-1 -methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl; haloalkenyl radical: straight or branched hydrocarbon radicals having 2 to 10 carbon atoms and one or two double bonds in arbitrary position (as mentioned above), the hydrogen atoms in these groups being partially or completely substituted by halogen atoms such as those mentioned above, especially fluorine, chlorine and bromine; alkynyl: linear or branched hydrocarbon groups with 2 to 4, 6, 8 or 10 carbon atoms and one or two triple bonds in arbitrary position, eg C2-C6-alkynyl, such as ethynyl, 1-propynyl, 2- propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1 -pentinyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl- 3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1, 1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexyl, 2-hexynyl, 3-hexynyl, 4-Hexynyl, 5-Hexynyl, 1-Methyl-2-Pentynyl, 1-Methyl-3-Pentynyl, 1-Methyl-4-Pentynyl, 2-Methyl-3-Pentynyl, 2-Methyl-4-Pentynyl, 3- methyl-1 -pentinyl, 3-methyl-4-pentynyl, 4-methyl-1 -pentinyl, 4-methyl-2-pentyne, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2- ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl; cycloalkyl: mono- or bicyclic hydrocarbon group with 3 to 6 saturated or 8 carbon ring members, eg C3-C8-cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, ciciohexilo, cicioheptilo and cyclooctyl; saturated, partially unsaturated or aromatic heterocycle with five to ten members, containing one to four heteroatoms of the group O, N or S: heterocyclyl of five or six membered, containing one to three nitrogen atoms and / or an oxygen atom or sulfur or one or two oxygen atoms and / or sulfur atoms, eg 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahidrotieniIo, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidiniIo, 5- soxazolidinilo, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5 -pirazolidinilo, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 2-pyrrolidin-2-yl, 2-pyrroline-3 -yl, 3-yl-2-pirrol¡n, 3-pyrroline-3-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1, 3-dioxan-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl , 2-tetrahydrothienyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl and 2-piperazinyl; five-membered heterocaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom: pentacyclic heteroaryl groups, which in addition to carbon atoms may contain one to four nitrogen atoms or one three nitrogen atoms and one sulfur or oxygen atom as ring members, eg 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, -pirazolilo, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, and 1, 3,4-triazol-2- ilo; six-membered heteroaryl, which contains one to three or one to four nitrogen atoms: heterocyclic hexacyclic groups, which in addition to carbon atoms may contain one to three or one to four nitrogen atoms as ring members, e.g. ., 2-pyridinyl, 3-pyridinium, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrimidinyl; As for the use to which the compounds II are intended, the following meanings of the substituents are preferred, both by themselves and also in combinations: R1 means hydrogen; R2 means CrCe-alkyl, such as, for example, methyl and ethyl, especially methyl, R3 means C ^ Ce-alkyl, such as, for example, methyl and ethyl, especially ethyl; R4 means C Ce-alkyl, especially methyl; R5 is CrC6-alkyl, especially methyl; m is 1, where R5 is in position para with respect to R4; A means oxygen (-O-); R6 means phenyl, which is preferably unsubstituted or can be substituted by one to three Rf groups, especially by one or two Rf groups; Rf means halogen, especially fluorine or chlorine, alkyl, especially methyl, ethyl, n- and iso-propyl and tere, butyl and haloalkyl, especially trifluoromethyl.

The Rf groups are preferably in positions 3 or 3.4.

For the intended use in admixture with compound I, the following compounds of the formula HA are especially suitable: The compounds I and II are able, thanks to the basic character of the nitrogen atoms contained therein, to form salts or adducts with inorganic or organic acids or with metal ions.

Examples of inorganic acids are the hydrohalic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid, sulfuric acid, phosphoric acid and nitric acid.

Suitable organic acids are, for example, formic acid, carbonic acid and alkanoic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, as well as glycolic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic, oxalic acid, p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid and 2-acetoxybenzoic acid.

As metal ions, especially the ions of the elements of the first to eighth secondary group, especially chromium, manganese, iron, cobalt, nickel, copper, zinc and, in addition, of the second main group, especially calcium and magnesium, are particularly suitable. , of the third and fourth main group, especially, aluminum, tin and lead. The metals can be present in the different valences that correspond to them.

Preferably, pure principles I and II are used in the preparation of the mixtures, to which, if necessary, other active ingredients can be added against harmful fungi or other pests, such as insects, arachnids or nematodes, or also active principles. herbicides or growth regulators or fertilizers.

Preferably, pure principles I and II are used in the preparation of the mixtures, to which, if necessary, other active ingredients can be added against harmful fungi or other pests, such as insects, arachnids or nematodes, or also active principles. herbicides or growth regulators or fertilizers.

Other active ingredients in the sense indicated above are, in particular, fungicides selected from the following groups: • acylalanines, such as benalaxyl, metalaxyl, ofurace, oxadixyl, • amine derivatives, such as aldimorf, dodin, dodemorf, phenpropimorf, fenpropidin, guazatin, iminoctadine, spiroxamine, tridemorph • anilinopyrimidines, such as pyrimethanil, mepanipyrim or cyprodinil, • antibiotics , such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin, • azoles, such as bitertanol, bromoconazole, ciproconazole, diphenoconazole, dinitroconazole, enilconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prochloraz, protioconazole, simeconazole, tebuconazole, tetraconazole, triadimefonone, triadimenol, triflumizole, triticonazole, • dicarboximides, such as prodrone, myclozoline, procymidone, vinclozoline, • dithiocarbamates, such as ferbam, nabam, maneb, mancozeb, metam, metiram, propineb, polycarbamate, thiram, ziram, zineb, • heterocyclic compounds, such as anilazin, benomyl, boscalide, carbendazim, carboxin, oxycarboxin, cyazofamide, dazomet, dithianone , famoxadone, fenamidone, fenarimol, fuberidazole, flutolanil, furametpir, isoprothiolane, mepronil, nuarimol, pentiopyrad, picobenzamide, probenazole, proquinazide, pirifenox, pyroquilone, quinoxifene, siltiofam, thiabendazole, thifluzamide, thiophanate-methyl, thiadinyl, tricyclazole, triforine, • copper fungicides, such as Bordeaux broth, copper acetate, copper oxychloride, basic copper sulfate, • nitrophenyl derivatives, such as binapacryl, dinocap, dinobutone, nitroftal- isopropyl • phenylpyrroles, such as phenpiclonyl or fludioxonil, • sulfur, • other fungicides, such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorothalonil, cyflufenamide, cymoxanil, diclomezine , diclocimet, dietofencarb, edifenfos, etaboxam, fenhexamida, fentina-acetate, fenoxanilo, ferimzona, fluacinam, fosetilo, fosetilo-aluminio, acid fosforoso, iprovalicarb, hexachlorobenzene, metrafenona, pencicurona, propamocarb, ftalida, toloclofos-methyl, quintozeno, zoxamida, • strobilurins, such as azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orisastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin, • sulfenic acid derivatives, such as captafol, captan, diclofluanide, folpet, tolylfluanide • cinnamic acid amides and analogs, such as dimetomorph, flumetover or flumorf.

In one embodiment of the mixtures according to the invention, another fungicide III or two fungicides III and IV are added to compounds I and 11.

Mixtures of compounds I and II with a component III are preferred.

Mixtures of compounds I and II are especially preferred.

Compound I and compound II are usually used in a weight ratio of 100: 1 to 1: 100, preferably, 20: 1 to 1: 20, especially 10: 1 to 1:10.

The components III and, optionally, IV are added, if desired, in a ratio of 20: 1 to 1: 20 to compound I.

The amounts of application for the mixtures according to the invention vary, depending on the type of compound and the desired effect of 5 g / ha to 1000 g / ha, preferably 50 to 900 g / ha, especially 50 to 750 g / ha.

The application rates for compound I range, correspondingly, as a rule, from 1 to 1000 g / ha, preferably from 10 to 900 g / ha, especially from 20 to 750 g / ha.

The application rates for compound II range, correspondingly, as a rule, from 1 to 1000 g / ha, preferably from 10 to 500 g / ha, especially from 40 to 350 g / ha.

In the treatment of the seeds, application amounts are generally used in the mixture of 1 to 1000 g / 100 kg of seeds, preferably 1 to 200 g / 100 kg, especially 5 to 100 g / 100 kg.

The process for combating harmful fungi is carried out by separately or jointly applying the compound I and the compound II or the mixtures of the compound and the compound II, by spraying or dusting the seeds, the plants or the soil before or after the sowing of the plants. plants or before or after the emergence of the plants.

The mixtures according to the invention or compounds I and II can be converted into the customary formulations, for example solutions, emulsions, suspensions, powders, pastes and granules. The form of application depends on the respective end of application, but in any case a fine and uniform distribution of the compound according to the invention must be ensured.

The formulations are prepared in a known manner, for example, by diluting the active principle with solvents and / or supports, if desired, using emulsifiers and dispersants. Suitable solvents / auxiliaries are substantially for this purpose: water, aromatic solvents (eg Solvesso products, xylene), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol) , pentanol, benzyl alcohol), ketones (eg cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, dimethylgreased acid amides, fatty acids and fatty acids. Basically, solvent mixtures can also be used, - carrier substances, such as natural stone powders (eg kaolins, clays, talc, chalk) and synthetic stone powders (eg highly disperse silicic acid, silicates); emulsifiers, such as non-ionogenic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants, such as sulphite residual liquors and methylcellulose.

Suitable surfactants are the alkali metal, alkaline earth metal and ammonium salts of lignin sulphonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutyl naphthalene sulfonic acid, alkylaryl sulphonates, alkyl sulfates, alkyl sulfonate, fatty alcohol sulfates, fatty acids and fatty alcohol glycol ethers sulphonates, in addition, sulfonated naphthalene condensates and naphthalene derivatives with formaldehyde, naphthalene or naphthalene sulfonic acid condensates with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl- polyglycol ether, alkylaryl polyether alcohol, condensates of alcohol and fatty alcohol / ethylene oxide, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, polyglycol ether acetal lauryl alcohol, sorbitol esters, lignin-sulf residual liquors ítics and methylcellulose.

Suitable substances for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are: fractions of mineral oil from medium boiling point to high, such as eg kerosene or diesel oil, in addition, coal tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, example, dimethyl sulfoxide, N-methylpyrrolidone and water.

Powders, spraying and spraying agents can be prepared by mixing or grinding together the active substances with a solid support.

Granules, eg coated, impregnated or homogeneous granules, can be prepared by coupling the active ingredient with a solid support. Examples of solid fillers are: mineral soils, such as silica gel, silicic acids, silicate gels, silicates, talc, kaolin, limestone, lime, bolus, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, oxide magnesium, ground plastics, as well as fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as cereal flour, bark, wood and nut powder, cellulose powder or other solid supports.

Generally, the formulations contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight of the active ingredients. The active ingredients are usually used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).

Examples of formulations according to the invention are: 1. Products for dilution in water A) Water-soluble concentrates (SL) 10 parts by weight of the active ingredients are dissolved in water or in a water-soluble solvent. Alternatively, humectants or other auxiliaries may be added. The active ingredient dissolves when it is diluted with water.

B) Dispersible Concentrates (DC) 20 parts by weight of the active ingredients are dissolved in cyclohexanone by adding a dispersant, for example, polyvinylpyrrolidone. Diluting with water, a dispersion is obtained.

C) Emulsifiable concentrates (EC) 15 parts by weight of the active ingredients are dissolved in xylene by adding calcium dodecylbenzenesulfonate and castor oil ethoxylate (5% respectively). Diluting with water, an emulsion is obtained.

D) Emulsions (EW, EO) 40 parts by weight of the active ingredients are dissolved in xylene by adding calcium dodecylbenzenesulfonate and castor oil ethoxylate (5% respectively). This mixture is introduced into water by means of an emulsifier (Ultraturrax) and transformed into a homogeneous emulsion. Diluting with water, an emulsion is obtained.

E) Suspensions (SC, OD) In a ball mill with agitator, 20 parts by weight of the active ingredients are comminuted by adding a dispersant, humectant and water or an organic solvent, obtaining a fine suspension of active ingredient. By diluting with water, a stable suspension of the active ingredient is obtained.

F) Water-dispersible granules and water-soluble granules (WG, SG) 50 parts by weight of the active ingredients are ground finely, adding dispersants and wetting agents, and transformed into water-dispersible or water-soluble granulates by means of technical devices (e.g. , extruder, spray tower, fluidized bed). By diluting with water, a dispersion or stable solution of the active principle is obtained.

G) Water-dispersible powders and water-soluble powders (WP, SP) 75 parts by weight of the active ingredients are ground in a rotor-stator mill by adding dispersant, humectants and silica gel. Diluting with water, a stable dispersion or solution is obtained with the active principle. 2. Products for direct application H) Powders (DP) 5 parts by weight of the active ingredients are ground finely and intimately mixed with 95% of a finely divided kaolin. A sprayable powder is obtained.

I) Granules (GR, FG, GG, MG) 0.5 parts by weight of the active ingredients are ground finely and associated with 95.5% support. Current methods are: extrusion, spray drying and fluidized bed. Granules are obtained that can be applied without dilution.

J) Ultra low volume solutions (UL) 10 parts by weight of the active ingredients are dissolved in an organic solvent, for example, xylene. A product is obtained that can be applied without dilution.

The active ingredients can be used as such, in the form of their formulations or the forms of application prepared therefrom, for example, as solutions, powders, suspensions or dispersions, emulsions, directly sprayable oil dispersions, pastes, sprayable powders. , spraying agent or watering agent. The forms of application depend entirely on the purpose of application, but in any case it is necessary to ensure a distribution as fine as possible of the active ingredients according to the invention.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, substances can be homogenized as such or dissolved in an oil or solvent in water with the aid of a humectant, adhesion promoter, dispersant or emulsifier. Alternatively, concentrates composed of the active substance, wetting agent, tackifier, dispersant or emulsifier, if appropriate, solvent or oil, can be prepared and such concentrates are suitable to be diluted with water.

The active substance concentrations in ready-to-use preparations can vary widely. In general, they vary between 0.0001 and 10%, preferably between 0.01 and 1%.

The active ingredients can also be used successfully in the ultra-low volume (ULV) process, formulations with more than 95% by weight of active ingredient, or even the active ingredient without additives, can be applied.

Several types of oil, humectants, adjuvants, herbicides, fungicides or other pesticides or bactericides can be added to the active ingredients, if necessary, just before application (tank mixture). These agents can be mixed with the agents according to the invention in a weight ratio of 1:10 to 10: 1.

The compounds I and II or the mixtures or corresponding formulations are applied, treating the noxious fungi, the plants, seeds, floors, surfaces, materials or enclosures to be kept free of the harmful fungi, with an active fungicidal quantity of the mixture or of the compounds I and II in the separate application. The application can be done before or after the infestation by the harmful fungi.

The fungicidal effect of the compounds and mixtures could be demonstrated in the following tests: The active ingredients were prepared separately as a stock solution with 25 mg of active principle, which was completed with a mixture of acetone and / or dimethyl sulfoxide and the emulsifier Uniperol® EL (emulsifier and dispersant humectant based on ethoxylated alkylphenols) in the solvent-emulsifier volume ratio of 99 to 1 ad 10 ml. Next, it was completed with water ad 100 ml. The active ingredients or mixtures were diluted or mixed with water according to the indicated concentration.

Efficiency against helminth infections of barley caused by Pyrenophora teres in the one-day protective application The leaves of barley seedlings of the "Hanna" variety grown in pots were sprayed until they dripped with an aqueous suspension of the concentration of active principle indicated below. 24 hours after the sprayed layer was dry, the test plants were inoculated with an aqueous suspension of Pyrenophora [syn. Drechslera] teres, the pathogen of helminthosporiosis. Next, the test plants were placed in the greenhouse at temperatures between 20 and 24 ° C and 95 to 100% relative humidity of the air. After six days, the development of the disease was visually evaluated in percent of the total leaf area.

The visually determined values for the percentage of the infected leaf surface were converted into action degrees as% of the untreated control: The degree of action (W) was calculated according to Abbot's formula in the following way: W = (1 - s / ^) A00 s is equivalent to the fungal infection of the plants treated in% and ß is equivalent to the fungal infection of the untreated plants (control) in% Given a degree of action equal to 0, the infection of the treated plants is equivalent to that of the untreated control plants; in case of an action degree of 100, the treated plants do not present any infestation.

The expected action levels of the mixtures of active principles are determined by means of the Coiby formula (Coiby, SR (Calculating synergistic and antagonistic responses of herbicide combinations, Weeds, 15, pp. 20-22, 1967) and compared with the observed degrees of action.

Coiby's formula: E = x + y - x-y / 100 E means the expected degree of action, translated in% of the untreated control, when using the mixture from the active principles A and B in the concentrations a and bx is the degree of action, translated in% of the untreated control, when using the active ingredient A in the concentration a and is the degree of action, translated in% of the untreated control, when using the active principle B in the concentration b.

Table A - Individual active principles Table B - Mixtures according to the invention *) degree of action calculated according to the Coiby formula From the results of the tests, it can be seen that the mixtures according to the invention, thanks to the strong synergism, are considerably more efficient than they had been precalculated according to the Coiby formula.

R6 is phenyl or a saturated, partially unsaturated or aromatic heterocyclic of five or six members, containing one to four heteroatoms of the group O, N or S; whose groups may be substituted in the manner indicated in the description; in a synergistically effective amount, method for combating harmful fungi with mixtures of compound I with compound II and the use of compound I with compound II for obtaining such mixtures, as well as products, containing these mixtures.

Claims (10)

Claims Fungicide mixtures to combat phytopathogenic noxious fungi, which contain

1) the triazolopyrimidine derivative of the formula 2) a phenylamidine derivative of the formula II, in which the variables have the following meanings: R1 is hydrogen, CrC8-alkyl, C2-C8-alkenyl or C2-C8-alkynyl, which do not carry substituents or can be substituted by one to three Ra groups: Ra is halogen, d-Cs-alkoxy, CrCa-halogenoalkoxy, C? -C8-alkylthio or phenyl, which may be substituted by halogen, d-Cß-alkyl, d-C8-haloalkyl, d-C8-alkoxy, C? -C8-haloalkoxy or C-C-alkylthio; R2, R3 can be the same or different radicals and represent hydrogen, cyano, CrC8-alkyl, C2-C8-alkenyl, C2-C8-aikinyl, d-C8-alkoxy, C C8-alkoxyalkyl, benzyloxy or d-d-alkylcarbonyl, which do not bear substituents or can be substituted by one to three Ra groups; R 4 is hydrogen, C C 8 -alkyl, C 2 -C 8 -alkenyl or C 2 -C 8 -alkynyl, which do not carry substituents or can be substituted by one to three groups Rb: Rb is one of the groups mentioned for Ra, cyano, C (= O) Rc, C (= S) RC or S (O) pRc, Rc is CrCß-alkyl, C-? - C8-haloalkyl, d-C8-alkoxy, d- Ca-halogenoalkoxy, d-C3-alkylthio, amino, d-C8-alkylamino, di (d-C8-alkyl) amino or phenyl, which may be substituted by halogen, d-C8-alkyl, d-Cβ-haloalkyl, d-C8-alkoxy, d-C8-haloalkoxy or d-C8-aicytthio; m is 0 or 1; R5 is one of the groups mentioned for R; A is a direct bond, -O-, -S-, NRa, CHRe or -O-CHRe; Rd, Re represent one of the groups mentioned for Ra; R6 is phenyl or a saturated, partially unsaturated or aromatic heterocyclic of five or six members, containing one to four heteroatoms of the group O, N or S, whose R6 groups do not bear substituents or can be substituted by one to three Rf groups: Rf is one of the groups mentioned for Rb or amino, C C8-alkylamino, dd-Cs-alkylamino, d-C8-haloalkyl, d-C8-alkoxyalkyl, C2-C8-alkenyloxyalkyl, C2-C8-alkynyloxyalkyl , C? -C8-alkylcarbonyloxy-C? -C8-alkyI, cyanooxy-C8-alkyl, C3-C6-cycloalkyl or phenoxy, the cyclic groups being able to be substituted by halogen, d-C8-alkyl , d-Ca-haloalkyl, d-C8-alkoxy, C-C8-haloalkoxy or d-Ca-alkylthio; in a synergistically effective amount.

2. Fungicidal mixtures according to claim 1, containing as a phenylamidine derivative a compound of the formula HA; wherein the variables have the following meanings: R2, R3 is methyl and ethyl; R, R5 is methyl; Rf, Rff is halogen, alkyl and haloalkyl.

3. Fungicidal mixtures according to one of claims 1 or 2, containing the compound of the formula I and the compound of the formula II in a weight ratio of 100: 1 to 1: 100.

4. Product, which contains a liquid or solid support and a mixture according to one of claims 1 to 3.

5. Process for combating phytopathogenic fungi, characterized in that the noxious fungi, their habitat or the plants, the soil or the seeds to be protected against them are treated with an effective amount of the compound I and of the compound II according to claim 1.

6. Process according to claim 5, characterized in that the compounds I and II according to claim 1 are applied simultaneously, namely, jointly or separately, or successively.

Process according to claims 5 or 6, characterized in that the compounds I and II according to claim 1 or the mixtures according to one of claims 1 to 3 are applied in an amount of 5 g / ha to 1000 g / he has.

Process according to one of claims 5 to 7, characterized in that the compounds I and 11 according to claim 1 or the mixture according to one of claims 1 to 3 are applied in an amount of 1 to 1000 g / 100. kg of seeds.

Seeds, which contain the mixture according to one of claims 1 to 3 in an amount of 1 to 1000 g / 100 kg.

10. Use of the compounds I and II according to claim 1 for obtaining a product suitable for combating harmful fungi. Summary The present invention relates to fungicidal mixtures, which contain as active components 1) the triazolopyrimidine derivative of the formula 2) a phenylamidine derivative of the formula II, in which the variables have the following meanings: R1, R4, R5 represent alkyl, alkenyl or alkynyl; R2, R3 represent cyano, alkyl, alkenyl, alkynyl, alkoxy, alkoxyalkyl, benzyloxy or alkylcarbonyl; m is 0 or 1; A is a direct bond, -O-, -S-, NRd, CHRe or -O-CHR6; R6 is phenyl or a saturated, partially unsaturated or aromatic heterocyclic of five or six members, containing one to four heteroatoms of the group O, N or S; whose groups may be substituted in the manner indicated in the description; in a synergistically effective amount, method for combating harmful fungi with mixtures of compound I with compound II and the use of compound I with compound II for obtaining such mixtures, as well as products, containing these mixtures.