EP1732389A1

EP1732389A1 - Fungicidal mixtures

Info

Publication number: EP1732389A1
Application number: EP05730057A
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: 2004-03-26
Filing date: 2005-03-22
Publication date: 2006-12-20
Also published as: US20080058352A1; ZA200608829B; NZ549848A; TW200600012A; AR049373A1; NO20064835L; BRPI0508683A; KR20060132015A; IL177655A0; WO2005092100A1; UY28820A1; CN1933731A; CA2558345A1; AU2005226883A1; JP2007530483A; EA200601675A1

Abstract

Fungicidal mixtures, containing the following as active components:1) a triazolopyrimidine derivative of formula I, and 2) an anilide of formula II, wherein the variables have the following meanings: Ar = phenyl or a five or six membered aromatic heterocycle, containing one to four heteroatoms, from the group consisting of O, N or S, wherein the cycles are unsubstituted or can be substituted by one to three R1 groups; R1 = halogen, alkyl or halogenalkyl; R = phenyl, alkyl, halogenalkyl, alkoxy, halogenalkoxy; Q = hydrogen, alkyl, halogenalkyl, alkoxy, halogenalkoxy; in a synergistically effective amount . The invention also relates to methods for combating noxious fungi with mixtures of compound I and compound II and to the use of compound I and compound II in the production of said mixtures, and to agents containing said mixtures.

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) an anilide of the formula II, in which the variables have the following meanings:

Ar phenyl or a five- or six-membered aromatic heterocycle containing one to four heteroatoms from the group O, N or S, where the cycles are unsubstituted or can be substituted by one to three groups R ¹ :

R ^{1 is} halogen, CC alkyl or C _r C haloalkyl;

R is phenyl, CC ₈ -alkyl, C _r C ₈ -haloalkyl, CC ₈ -alkoxy, CC ₈ -haloalkoxy;

Q is hydrogen, CrC ₈ alkyl, C _r C ₈ haloalkyl, -C ₈ alkoxy, CC ₈ haloalkoxy;

in a synergistically effective amount.

The invention also relates to a method for controlling harmful fungi using mixtures of the compound I with the compound II and the use of the compound fertilizer I with the compound II for the preparation 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-azolo [1, 5 -a] pyrimidine, its preparation and its action against harmful fungi is known from the literature (WO 98/46607).

The compounds II, their preparation and their action against harmful fungi are also known from the literature (JP 10130268).

Mixtures of triazolopyrimidines with other active ingredients are generally known from EP-A 988 790 and US 6 268371.

Mixtures of compounds II with other active ingredients are known, for example, from JP 11228309, JP 2000053506 and JP 2001072513.

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 one of the compounds II are used jointly or separately, or when the compound I and one of the compounds II are used in succession, harmful fungi can be controlled more effectively than with the individual compounds.

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, Oomycetes and Basidiomycetes. They can be used in plant protection as leaf 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 particularly suitable for combating the following phytopathogenic fungi: Blumeria graminis (powdery mildew) on cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants, Podosphaera leucotricha on apples, Uncinula necatoran vines, Puccinia species on cereals, Rhizolea species - le, rice and lawn, Ustilago species on cereals and sugar cane, Venturia inaequalis on apples, Bipolaris and Drechslera species on cereals, rice and lawn, Septoria nodrum on wheat, Botrytis cinerea on strawberries, vegetables, ornamental plants and vines , My- cosphaerella-Aüen on bananas, peanuts and cereals, Pseudocercosporella her- potrichoides on wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Pseudoperonospora arias on pumpkin plants and hops, Plasmopara viticola-Aύ on vines, Altern in vegetables and fruits as well as Fusaria and Verticillium species.

They can also be used in material protection (e.g. wood protection), for example against Paecilomyces variotii.

The compound I and the compounds 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 variables given in formula II, collective terms were used which are generally representative of the following substituents:

Halogen: fluorine, chlorine, bromine and iodine;

Alkyl: saturated, straight-chain or branched hydrocarbon radicals with 1 to 4, 6 or 8 carbon atoms, for example CC ₆ alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1- Dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 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: straight-chain or branched alkyl groups with 1 to 2, 4, 6 or 8 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 CC ₂ haloalkyl such as chloromethyl, bromomethyl , Dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluorine ethyl, 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 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-furyi, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, and 1, 3,4-triazol-2-yl;

6-membered heteroaryl containing one to three or one to four nitrogen atoms: 6-ring heteroaryl groups which, in addition to carbon atoms, can contain one to three or one to four nitrogen atoms as ring members, e.g. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl;

The scope of the present invention includes the (R) and (S) isomers and the racemates of compounds of the formula I which have chiral centers.

With regard to their intended use of the compounds II, the following meanings of the substituents, in each case individually or in combination, are particularly preferred:

Ar preferably denotes phenyl or a five-membered aromatic heterocycle, in particular a five-membered heteroaryl residue which is unsubstituted or substituted by one or two groups R ¹ .

In addition, Ar preferably represents the following groups: phenyl, pyridine, pyrazine, furan, thiophene, pyrazole and thiazole. Particularly preferred groups Ar are: 3-pyridinyl, pyrazinyl, 3-furyl, 3-thiophenyl, 4-pyrazolyl, 5-thiazolyl.

A group R ^{1 is} particularly preferably in the ortho position to the amide group.

Preferred groups R ¹ are halogen, in particular chlorine, alkyl, in particular methyl, and halomethyl, in particular fluoromethyl, difluoromethyl or trifluoromethyl.

Preferred groups R are alkyl groups, especially branched C ₃ -C ₈ alkyl groups, especially 4-methyl-pent-2-yl. The following compounds of the formula II are particularly suitable for the intended use in a mixture with the compound I:

If two groups R ¹ are present in a formula, these groups can be the same or different.

Compounds IIA, in particular compounds of the formulas IIA.1 and IIB.1, in which R can be the same or different and are methyl and halomethyl and R is alkyl, such as branched C ₃ -C ₈ -alkyl, in particular 4- methyl-pent-2-yl:

Compounds IIA.11 (common name: penthiopyrad) and IIB.11, which are in the form of their R and S isomers, are particularly preferred:

Because of the basic character of the nitrogen atoms they contain, the compounds I and II are able to form salts or adducts with inorganic or organic acids or with metal ions. Examples of inorganic acids are hydrohalic acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, sulfuric acid, phosphoric acid and nitric acid.

Examples of organic acids are formic acid, carbonic acid and alkanoic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid benzoic acid and 2-acetoxybenzoic acid into consideration.

In particular, the ions of the elements of the first to eighth subgroups, in particular chromium, manganese, iron, cobalt, nickel, copper, zinc and in addition the second main group, in particular calcium and magnesium, the third and fourth main group, in particular aluminum, tin and, come as metal ions Lead into consideration. The metal ions can optionally be present in different valences.

In the preparation of the mixtures, preference is given to using the pure active ingredients I and II, to which, as required, further active ingredients against harmful fungi or other pests such as insects, arachnids or nematodes, or else herbicidal or growth-regulating active ingredients or fertilizers can be admixed.

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, fuberidazole, flutolanil, furametpyr, isoprothiolan, mepronazolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, nuquin Pyroquilon, quinoxyfen, silthofam, thiabendazole, thifluzamide, thiophanate-methyl, tiadinil, tricyclazole, triforins,

Copper fungicides such as Bordeaux broth, copper acetate, copper oxychloride, basic copper sulfate,

• Nitrophenyl derivatives, such as binapacryl, dinocap, dinobuton, nitrophthal-isopropyl

• phenylpyrroles such as fenpiclonil or fludioxonil, • sulfur

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

• Strobilurins such as azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, cresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin, • Sulphonic acid derivatives such as Captafol, Captan, dichlofluanfluanid, folpet

• 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 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. Accordingly, the application rates for the compound I are 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 500 g / ha, in particular from 40 to 350 g / ha.

In the case of seed treatment, application rates of mixture of 1 to 1000 g / 100 kg of seed, preferably 1 to 200 g / 100 kg, in particular 5 to 100 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 emergence of the plants. Application is preferably carried out by spraying the leaves.

The mixtures according to the invention, or the compounds I and II, can be converted into the customary formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules. The form of application 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 suitable as solvents / auxiliaries: water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example petroleum fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example 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 liquors and methyl cellulose.

Alkali, alkaline earth, and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid come as surface-active substances, Alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, Nonylphenol, alkylphenol polyglycol ether, tributylphenyl polyglycol ether, tristerylphenyl polyglycol ether, alkyl aryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbyl glycol ether acetal, l-sorbitol ether glycolate, sorbitol, glycolorbitol lignite, glycolorbitol lignite, glycolorbitol lignite, glycolorbitol lignite, glycolorbitol lignite, glycolorbitol lignite, glycolorbitol lignite, and methylglycol ether acetal, lorbate, glycolorbitol lignin, glycolorbitol, and methylglycol ether acetal.

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% each). 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% each). 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 are comminuted in a stirred ball mill to form a fine active ingredient suspension with the addition of dispersing and wetting agents and water or an organic solvent. Dilution in water results in a stable suspension of the active ingredient.

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 using technical equipment (e.g. extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. 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 finely ground 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. 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 composed 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 can be demonstrated by the following tests:

The active ingredients were prepared separately or together 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 to 10 ml was filled. Then ad 100 ml was made up with water. This stock solution was diluted with the solvent-emulsifier-water mixture described to the active substance concentration given below. Alternatively, the active ingredients were used as a commercial finished formulation and diluted with water to the stated active ingredient concentration.

Example of use - Efficacy against barley mesh stain caused by Pyrenophora teres after 5 days of protective use

Leaves of barley seedlings grown in pots were sprayed to runoff point with an aqueous suspension in the active compound concentration given below. 5 days after the application, the test plants were treated with an aqueous spore suspension of Pyrenophora [syn. Drechslern] 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:

W = (1 - σ / yff) - 100 a 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, SR (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 - xy / 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 ay, the efficiency, expressed in% of the untreated control when using the active ingredient B in the concentration b

Table A - Individual substances

Table B - mixtures according to the invention

*) Efficiency calculated according to the Colby formula

The results of the experiments show that, due to the strong synergism, the mixtures according to the invention are significantly more effective in all mixing ratios than calculated in advance using the Colby formula.

Claims

claims

1. Containing fungicidal mixtures for controlling phytopathogenic harmful fungi

1) the triazolopyrimidine derivative of the formula I,

and 2) an anilide of formula II, in which the variables have the following meanings:

R ^{1 is} halogen, CC ₄ alkyl or CC ₄ haloalkyl;

R phenyl, C _r C ₈ alkyl, C Cs haloalkyl, CrCs alkoxy, CC ₈ haloalkoxy;

Q is hydrogen, CC ₈ alkyl. CC ₈ haloalkyl, CC ₈ alkoxy, CC ₈ haloalkoxy; in a synergistically effective amount.

2. Fungicidal mixtures according to claim 1, containing as the anilide a compound of the formulas IIA.1 or IIB.1; in which R ¹ can be the same or different and represents methyl and halomethyl and R represents alkyl.

3. Fungicidal mixtures according to one of claims 1 or 2, containing as anilide penthiopyrad of the formula IIA.11

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

5. Agent containing a liquid or solid carrier and a mixture according to one of claims 1 to 4.

6. 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.

7. The method according to claim 6, characterized in that the compounds I and II according to claim 1 simultaneously, jointly or separately, or in succession.

8. The method according to claims 6 or 7, characterized in that the compounds I and II according to claim 1 or the mixtures according to one of claims 1 to 4 in an amount of 5 g / ha to 1000 g / ha.

9. The method according to any one of claims 5 to 7, characterized in that the compounds I and II according to claim 1 or the mixture according to one of claims 1 to 4 is used in an amount of 1 to 1000 g / 100 kg of seed.

10. Seed containing the mixture according to one of claims 1 to 4 in an amount of 1 to 1000 g / 100 kg.

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