EP1755398A2

EP1755398A2 - Fungicide mixtures made from a triazolpyrimidine derivative and biphenylamides

Info

Publication number: EP1755398A2
Application number: EP05740044A
Authority: EP
Inventors: Jordi Tormo I Blasco; Thomas Grote; Maria Scherer; Reinhard Stierl; Siegfried Strathmann; Ulrich Schöfl; Markus Gewehr
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2004-05-13
Filing date: 2005-05-11
Publication date: 2007-02-28
Also published as: EA200602022A1; AR049171A1; ZA200610327B; IL178695A0; WO2005110089A3; US20070197556A1; CN1972595A; UY28900A1; UA81731C2; JP2007537192A; NO20065543L; TW200614916A; ECSP067012A; WO2005110089A2; KR20070011598A; MXPA06012071A; MA28650B1; EG24520A; CR8708A; CA2563814A1

Abstract

The inventive fungicide mixtures contain as active components 1) a triazolopyrimidine derivative of formula (I) and at least on type of biphenyl amide of formula (II) wherein variables have the following designations: A is oxathiin- or 5-membered heteroaryl containing one or four nitrogen atoms and/or three nitrogen atoms and/or one sulphur or oxygen atom, wherein A is substitutable according to the description, R1 is hydrogen, alkyl, alkylcarbonyl or a carbonyl bonded group A, Ra and Rb are halogen, cyano, alkyl, halogenalkyl, alkoxycarbonyl, alkoxy, halogenalkoxy, alkylthio, alkylcarbonyl, formyl, alkylene- or alkenylene which connects two adjacent carbon atoms, m is 0, 1, 2, 3, 4 or 5, n is 0, 1 or 2, wherein the fungicide mixtures contain said components in the synergistically effective amount. A method for controlling pathogenic fungi using the mixtures of the compounds (I) and (II), the use of the compounds (I) and (II) for producing such mixtures and mixture-containing agents are also disclosed.

Description

Fungicidal mixtures

description

The present invention relates to fungicidal mixtures containing as active components

1) the triazolopyrimidine derivative of the formula I,

and

2) at least one biphenylamide of the formula II,

in which the variables have the following meaning: A oxathiin or 5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and / or one sulfur or oxygen atom, where A can be substituted by one or two identical or different substituents R. ; R halogen, cyano, dC ₄ alkyl, C Ca haloalkyl, CC ₄ alkoxy, CC ₄ alkylthio; R is hydrogen, CrC ₄ alkyl, CrC ₄ alkylcarbonyl or a group A bonded via carbonyl; R ^a , R ^b independently of one another halogen, cyano, CC ₄ alkyl, C -C ₄ haloalkyl, CrCe alkoxycarbonyl, CrC ₄ alkoxy, CC ₄ haloalkoxy, C ₁ -C ₄ alkylthio, CC ₄ alkylcarbonyl, Formyl, -CC ₄ alkylene or C ₂ -C ₄ alkenylene, which connects two adjacent carbon atoms; m 0, 1, 2, 3, 4 or 5, where R ^{a can be the} same or different if n is greater than 1, n 0, 1 or 2; where R ^{b may be the} same or different when n is 2; in a synergistically effective amount.

In addition, the invention relates to a method for controlling harmful fungi with mixtures of the compound I with a compound II and the use of the compound I with compounds II for the production of such mixtures and agents which contain these mixtures.

The compound I, 5-chloro-7- (4-methyl-piperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] tri-azo! O [1 , 5-a] pyrimidine, their preparation and their action against harmful fungi is known from the literature (WO 98/46607).

The compounds of formula II, their preparation and their action against harmful fungi are also known from the literature (WO 01/42223; DE 19840 322; JP 07/145 156; JP 2001/302605; WO 03/066609; WO 03/066610; WO 03/099803; WO 03/099804; DE-A 10246 959).

Mixtures of triazolopyrimidines with other active ingredients are generally known from EP-A 988790 and US 6 268 371.

With a view to reducing the application rates and widening the spectrum of action of the known compounds, the present invention was based on mixtures which, with a reduced total amount of active compounds applied, have an improved activity against harmful fungi (synergistic mixtures).

Accordingly, the mixtures defined at the outset were found. It has also been found that, when the compound I and the compound II are used simultaneously or separately, or when the compound I and the compound II are used in succession, harmful fungi can be combated better than with the individual compounds (synergistic mixtures).

The mixtures of the compound I and the compound II or the simultaneous joint or separate use of the compound I and the compound II are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromyces ten, Oomycetes and Basidiomycetes. They can be used in plant protection as leaf, pickling and soil fungicides. They are particularly important for combating a large number of fungi on various crops such as bananas, cotton, vegetables (e.g. cucumbers, beans and squashes), barley, grass, oats, coffee, potatoes, corn, fruit plants, rice, rye, soybeans, tomatoes , Wine, wheat, ornamental plants, sugar cane and a variety of seeds.

They are advantageously suitable for combating the following phytopathogenic fungi: Blumeria graminis (powdery mildew) on cereals, Erysiphe cichoracearum and Sphae-rotheca fuliginea on pumpkin plants, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia Aύen on cereals Cotton, rice and lawn, Ustilago seeds on cereals and sugar cane, Venturia inaequalis on apples, Bipolaris and Drechslera seeds on cereals, rice and grass, Sepfo / va species on wheat, Botrytis cinerea on strawberries, vegetables, ornamental plants and vines , Mycosphaerel / a species on bananas, peanuts and cereals, Pseudocercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice, Phakopsora-Aύen on soy, Phytophthora infestans on potatoes and tomatoes, Pseudoperonospora-A on pumpkin plants and hops Plasmopara viticola on vines, Alternaria Aύs on vegetables and fruits and Fusarium and Verticillium Aύs.

In particular, they are suitable for combating harmful fungi from the Oomycetes class. They can also be used in material protection (e.g. wood protection), for example against Paecilomyces variotii.

The compound I and the compound II can be applied simultaneously together or separately or in succession, the sequence in the case of separate application generally not having any effect on the success of the control measures.

In the definitions of the symbols given for formula II, collective terms were used which stand for the following substituents:

Halogen: fluorine, chlorine, bromine and iodine;

Alkyl: saturated, straight-chain or branched hydrocarbon radicals with 1 to 4 carbon atoms, for example CC ₄ alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl, 1,1-dimethylethyl;

Haloalkyl: straight-chain or branched alkyl groups with 1 or 2 carbon atoms (as mentioned above), in which case the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms as mentioned above: in particular CrC ₂ haloalkyl such as chloromethyl, bromomethyl, dichloromethyl, tri- chloromethyl, 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.

5-membered heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and / or one sulfur or oxygen atom: 5-ring heteroaryl groups which, in addition to carbon atoms, contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members can, e.g. 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazo-iyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyI, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, and 1,3,4-triazol-2-yl;

Alkylene: divalent unbranched chains from 1 to 4 CH ₂ groups, for example CH ₂ , CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ and CH ₂ CH ₂ CH ₂ CH ₂ ;

Alkenylene: divalent unbranched chains of 2 to 4 carbon atoms and one or two double bonds, for example CH = CH, CH = CHCH ₂ , CH = CH ₂ CH ₂ CH ₂ , CH ₂ CH = CH ₂ CH ₂ and CH = CHCH = CH;

Formula II particularly represents compounds in which the index n denotes 1 or 2, preferably 1.

In one embodiment of the mixtures according to the invention, the biphenyl amides correspond to the formula IIA:

in which (R ^a ) _m and (R ^b ) _{n are} as defined for formula II.

Compounds of the formula IIA in which n is 0 or 1 are preferred, where, if n is 1, the group R ^{b is} advantageously in the 4-position. Compounds IIA in which n = 0 are particularly preferred. In addition, compounds of the formula IIA in which m is 1 or 2 are also preferred, a substituent in the para position advantageously being present.

R ^a is preferably selected from the following groups: halogen, such as fluorine, chlorine, bromine; cyano; CC ₄ alkyl, such as methyl; -C-C ₄ haloalkyl, such as trifluoromethyl; CC - Alkoxy such as methoxy; CC ₄ haloalkoxy such as trifluoromethoxy; CC ₄ alkylthio, such as methylthio.

The following compounds of the formula IIA are particularly preferred:

In a further preferred embodiment of the mixtures according to the invention, the biphenylamides correspond to the formula IIB:

in which the variables are as defined for Formula II. Compounds of the formula IIB are preferred in which R is halomethyl, in particular difluoromethyl or trifluoromethyl. In addition, compounds IIB are preferred in which R ^{1 is} hydrogen, methyl, acetyl or 2-methyl, 4-difluoromethyl-thiazol-5-yl-carbonyl, in particular hydrogen.

Equally preferred are compounds IIB in which R ^{a is} halogen, cyano, methyl, methoxy, halomethyl, such as trifluoromethyl or halomethoxy such as trifluoromethoxy.

In addition, compounds IIB in which R ^{b is} halogen are preferred.

Compounds IIB in which n = 0 are also preferred.

In addition, compounds IIB in which m is 1 or 2 are preferred, a substituent in the para position advantageously being present.

The following compounds of the formula IIB are particularly preferred:

In a further preferred embodiment of the mixtures according to the invention, the biphenylamides correspond to the formula IIC:

in which the variables are as defined for Formula II.

The preferred configurations of the substituents of the compounds IIC correspond to those of the compounds IIB, where R ^{1 is} preferably hydrogen, methyl, acetyl or 2-methyl-furan-3-yl-carbonyl, in particular hydrogen.

In a further preferred embodiment of the mixtures according to the invention, the biphenylamides correspond to the formula HD:

in which the variables are as defined for formula II and R 'corresponds to a group R.

Compounds HD are preferred in which R represents halogen, in particular fluorine, methyl or halomethyl, such as trifluoromethyl. In addition, compounds HD are preferred in which R ^{1 is} preferably hydrogen or methyl, in particular hydrogen.

The preferred embodiments of the formula HD of (R ^a ) _m and (R ^b ) _n correspond to the formula IIB.

The following compounds HD are particularly preferred (R = H; n = 0):

When preparing the mixtures, preference is given to using the pure active ingredients I and II, to which, depending on the need, further active ingredients against harmful fungi or others Pests such as insects, arachnids or nematodes, or herbicidal or growth-regulating active ingredients or fertilizers.

Fungicides selected from the following group are particularly suitable as further active ingredients in the above sense:

Acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl,

Amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, 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, cyproconazole, difenoconazole, dinitroconazole, enilconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazol, penocolazolol, myocazolol, myocazolol, myclazol, myclazol, myclazol, myocazolol, myclazol, myclazol, myclazol, myclazol, myclazol , Tetraconazole, tri-dimefon, triadimenol, triflumizole, triticonazole,

Dicarboximides such as iprodione, myclozolin, procymidone, vinclozolin,

Dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamat, Thiram, Ziram, Zineb,

• Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet, dithianon, famoxadone, fenamidon, fenarimol, isoprothiolan, pentazolidolid, prozolidolid, prozolid Pyrifenox, pyroquilon, quinoxyfen, silthiofam, thiabendazole, thifluzamide, thiophanate-methyl, tiadinil, tricyclazole, triforine,

Copper fungicides such as Bordeaux broth, copper oxychloride, copper hydroxide, copper oxide, (basic) copper sulfate, copper oxychloride sulfate,

Nitrophenyl derivatives, such as binapacryl, dinocap, dinobutone, nitrophthal-isopropyl, phenylpyrroles such as fenpiclonil or fludioxonil,

• sulfur,

• Other fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorothalonil, cyflufenamid, cymoxanil, diclomezin, diclocymet, diethofencarb, edifenphos, ethaboxam, fenhexamide, fentin acetate, fenoxanil, namimzone, fluimazosi, fluazi, fluazi Fosetyl aluminum, iprovalicarb, hexachlorobenzene, mandipropamide, metrafenone, pencycuron, propamocarb, phosphorous acid, phthalide, toloclofos-methyl, quintozene, zoxamide,

Strobilurins such as azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, cresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin, Sulfenoic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid,

• Cinnamic acid amides and analogues such as dimethomorph, flumetover or flumorph.

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

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

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

If desired, components III and, if appropriate, IV are mixed in a ratio of 20: 1 to 1:20 to compound I.

Depending on the type of compound and the desired effect, the application rates of the mixtures according to the invention are 5 g / ha to 1000 g / ha, preferably 50 to 900 g / ha, in particular 50 to 750 g / ha.

The application rates for the compound I are accordingly generally from 1 to 1000 g / ha, preferably from 10 to 900 g / ha, in particular from 20 to 750 g / ha.

Correspondingly, the application rates for compound II are generally from 1 to 1000 g / ha, preferably from 10 to 900 g / ha, in particular from 40 to 500 g / ha.

In the case of seed treatment, application rates of mixture of 1 to 1000 g / 100 kg of seed, preferably 1 to 750 g / 100 kg, in particular 5 to 500 g / 100 kg, are generally used.

The method for controlling harmful fungi is carried out by the separate or joint application of the compound I and the compound II or the mixtures of the compound I and the compound II by spraying or dusting the seeds, the plants or the soil before or after the plants are sown or before or after. On the run of the plants.

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

The formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants. The following are essentially considered as solvents / auxiliaries:

- Water, aromatic solvents (e.g. Solvesso products, xylene), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol, pentanol, benzyl alcohol), ketones (e.g. cyclohexanone, gamma-butryolactone), pyrrolidones (NMP, NOP), Acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters. In principle, solvent mixtures can also be used

- Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste liquors and methyl cellulose.

Alkali, alkaline earth, and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated naphthalene naphthalene and sulfonated dehydrogenated naphthalene derivatives of sulfonated formaldehyde derivatives and sulfonated dehydrogenated naphthalenedaphthalene from sulfonates, as well as condensation products with sulfated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene ether and condensation products , Condensation products of naphthalene or of naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tri-butylphenyl polyglycol ether, trihylphenyl polyglycol ether, alkyl alcoholoxy ethoxylated alcohol, alkyl alcoholoxy ethoxylated alcohol , Laurylalkoholpolyglykoletheracetal, sorbitol ester, lignin sulfite waste liquors and methyl cellulose into consideration.

For the production of directly sprayable solutions, emulsions, pastes or oil dispersions, mineral oil fractions from medium to high boiling points, such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, e.g. Dimethyl sulfoxide, N-methylpyrrolidone or water into consideration.

Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier. Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are, for example, mineral earths, such as silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as ammonium sulfate, ammonium phosphate , Ammonium nitrate, ureas and vegetable products such as corn flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.

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

Examples of formulations 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 a water-soluble solvent. Alternatively, wetting agents or other aids are added. The active ingredient dissolves when diluted in water.

B) Dispersible concentrates (DC)

20 parts by weight of the active ingredients are dissolved in cyclohexanone with the addition of a dispersing agent e.g. Dissolved polyvinyl pyrrolidone. When diluted in water, a dispersion results.

C) Emulsifiable concentrates (EC)

15 parts by weight of the active ingredients are dissolved in xylene with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (5% in each case). Dilution in water results in an emulsion.

D) Emulsions (EW, EO)

40 parts by weight of the active ingredients are dissolved in xylene with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (5% in each case). This mixture is introduced into water using an emulsifying machine (Ultraturax) and brought to a homogeneous emulsion. Dilution in water results in an emulsion.

E) Suspensions (SC, OD) 20 parts by weight of the active ingredients with the addition of dispersants and wetting agents Crushed water or an organic solvent in a stirred ball mill to a fine active ingredient suspension. Dilution in water results in a stable suspension of the active ingredient.

i F) Water-dispersible and water-soluble granules (WG, SG) 50 parts by weight of the active ingredients are finely ground with the addition of dispersing and wetting agents and produced as water-dispersible or water-soluble granules by means of technical equipment (e.g. extrusion, spray tower, fluidized bed). Dilution in water results in a stable dispersion or solution of the active ingredient.

G) Water-dispersible and water-soluble powders (WP, SP) 75 parts by weight of the active ingredients are ground in a rotor-strator mill with the addition of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient.

2. Products for direct application

H) Dusts (DP) 5 parts by weight of the active ingredients are ground finely and mixed internally with 95% finely divided kaolin. This gives a dust.

I) Granules (GR, FG, GG, MG) 0.5 part by weight of the active ingredients are finely ground and combined with 95.5% carriers. Common processes are extrusion, spray drying or fluidized bed. This gives granules for direct application.

J) ULV solutions (UL) 10 parts by weight of the active ingredients are dissolved in an organic solvent e.g. Xylene dissolved. This gives you a product for direct application.

The active ingredients as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprinkling agents, granules by spraying, atomizing, dusting, scattering or pouring. The application forms depend entirely on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water the. To prepare emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, it is also possible to prepare concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.

The active ingredient concentrations in the ready-to-use preparations can be varied over a wide range. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.

The active ingredients can also be used with great success in the ultra-low-volume process (ULV), it being possible to apply formulations with more than 95% by weight of active ingredient or even the active ingredient without additives.

Oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides can be added to the active compounds, if appropriate also only immediately before use (tank mix). These agents are usually added to 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 the corresponding formulations, are used in that the harmful fungi, the plants, seeds, soils, surfaces, materials or spaces to be kept free of them are mixed with a fungicidally effective amount of the mixture or Compounds I and II treated separately. The application can take place before or after the infestation by the harmful fungi.

The fungicidal activity of the compound and the mixtures was demonstrated by the following tests:

The active ingredients were prepared separately as a stock solution with 25 mg of active ingredient which was mixed with a mixture of acetone and / or DMSO and the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) in a volume ratio of solvent emulsifier from 99 to 1 ad 10 ml was filled. Then ad 100 ml was made up with water. The active substances or mixtures were diluted or mixed with water in accordance with the stated concentration. Example of use - Effectiveness against barley mesh stain caused by Pyrenophora teres with 1 day protective application

Leaves of potted barley seedlings of the "Hanna" variety were sprayed to runoff point with an aqueous suspension in the active ingredient concentration given below. 24 hours after the spray coating had dried on, the test plants were sprayed with an aqueous spore suspension of Pyrenophora [syn. Drechslera] teres, the causative agent of net spot disease. The test plants were then placed in the greenhouse at temperatures between 20 and 24 ° C. and 95 to 100% relative atmospheric humidity. After 6 days, the extent of the development of the disease was determined visually in% of the total leaf area.

The visually determined values for the percentage of leaf areas affected were converted into efficiencies as% of the untreated control:

Efficiency (W) is calculated using Abbot's formula as follows:

α corresponds to the fungal attack of the treated plants in% and ß corresponds to the fungal attack of the untreated (control) plants in%

With an efficiency of 0, the infection of the treated plants corresponds to that of the untreated control plants; with an efficiency of 100, the treated plants show no infection.

The expected efficacies for combinations of active ingredients were determined using the Colby formula (Colby, S.R. (Calculating synergistic and antagonistic responses of herbicide combinations ", Weeds, 15, pp. 20-22, 1967) and compared with the observed efficacies.

Colby formula: E = x + y - x-y / 100

E expected efficiency, expressed in% of the untreated control, when using the mixture of active ingredients A and B in concentrations a and bx the efficiency, expressed in% of the untreated control, when using active ingredient A in concentration a the efficiency, expressed in% of the untreated control, when using the active ingredient B in the concentration b

Table A - Individual substances

*) Efficiency calculated according to the Colby formula

The results of the experiments show that the mixtures according to the invention are considerably more effective due to a strong synergism than calculated in advance using the Colby formula.

Claims

claims

1. Containing fungicidal mixtures for controlling harmful fungi

i 1) the triazolopyrimidine derivative of the formula I,

and

2) at least one biphenylamide of the formula II,

in which the variables have the following meaning: A oxathiin or 5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and / or one sulfur or oxygen atom, where A can be substituted by one or two identical or different substituents R; R halogen, cyano, CrC ₄ alkyl, C ₁ -C ₂ haloalkyl, CC ₄ alkoxy, CC ₄ alkylthio; R ^{1 is} hydrogen, C ¹ -C ₄ -alkyl, CC ₄ -alkylcarbonyl or a group A bonded via carbonyl; R ^a , R ^b independently of one another halogen, cyano, C ^ C ^ alkyl, CC ₄ -haloalkyl, CrC ₆ -alkoxycarbonyl, CC ₄ -alkoxy, CC ₄ -haloalkoxy, CrG _t -alkylthio, CrC ₄ -alkylcarbonyl, formyl , CC ₄ alkylene or C ₂ - C ₄ alkenylene, which connects two adjacent carbon atoms; m 0, 1, 2,

3, 4 or 5, where R ^{a can be the} same or different if n is greater than 1, n 0, 1 or 2; where R ^{b may be the} same or different when n is 2; in a synergistically effective amount. Fungicidal mixtures according to claim 1, containing a compound of formula IIA

in which (R ^a ) _m and (R ^b ) _{n have} the meaning according to Claim 1.

Fungicidal mixtures according to Claim 1, containing a compound of the formula IIB

in which the variables have the meaning according to claim 1.

4. Fungicidal mixtures according to claim 1, containing a compound of formula IIC

in which the variables have the meaning according to claim 1.

5. Fungicidal mixtures according to claim 1, containing a compound of formula HD

in which the variables have the meaning according to claim 1 and R 'corresponds to a group R.

6. Fungicidal mixtures according to one of claims 1 to 5, containing the compound of formula I and the biphenylamide in a weight ratio of 100: 1 to 1: 100.

7. Composition containing a liquid or solid carrier and a mixture according to one of claims 1 to 6.

8. A method for controlling phytopathogenic harmful fungi, characterized in that the fungi, their habitat or the plants to be protected against fungal attack, the soil or seeds are treated with an effective amount of the compound I and the compound II according to claim 1.

9. The method according to claim 8, characterized in that the compounds I and II according to claim 1 are applied simultaneously, that is jointly or separately, or in succession.

10. The method according to claims 8 or 9, characterized in that the compounds I and II according to claim 1 or the mixtures according to one of claims 1 to 6 in an amount of 5 g / ha to 1000 g / ha.

11. The method according to any one of claims 8 or 9, characterized in that the compounds I and II according to claim 1 or the mixture according to one of claims 1 to 6 in an amount of 1 to 1000 g / 100 kg of seed.

12. Seed containing the mixture according to one of claims 1 to 6 in an amount of 1 to 1000 g / 100 kg.

13. Use of the compounds I and II according to claim 1 for the preparation of a suitable agent for controlling harmful fungi.