EP1562428A1

EP1562428A1 - Fungicidal mixtures based on a triazolopyrimidine derivative and azoles

Info

Publication number: EP1562428A1
Application number: EP03814404A
Authority: EP
Inventors: Jordi Tormo I Blasco; Thomas Grote; Eberhard Ammermann; Reinhard Stierl; Siegfried Strathmann; Ulrich Schöfl
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2002-11-15
Filing date: 2003-11-14
Publication date: 2005-08-17
Also published as: BR0316273A; ECSP055760A; NO20051926L; CN1711019A; US20060111320A1; CO5570637A2; AP2005003312A0; RS20050358A; PL377178A1; KR20050075002A; EG23743A; AU2003303097A1; MA27494A1; AR042055A1; UA80731C2; JP2006517521A; CA2505588A1; CR7837A; MXPA05004548A; OA12956A

Abstract

Disclosed are fungicidal mixtures containing A) a triazolopyrimidine derivative of formula (I), and B) an azole derivative or the salts or addition compound thereof selected among bromuconazole, difenoconazole, diniconazole, fenbuconazole, fluquinconazole, flusilazole, hexaconazole, prochloraz, tetraconazole, triflumizole, flutriafol, myclobutanil, penconazole, simeconazole, ipconazole, triticonazole, and prothioconazole as active components in a synergistically effective quantity, methods for controlling plant-pathogenic fungi by means of mixtures of compounds I and II-XVIII, substances containing said mixtures, and the use of compounds I and II-XVIII for producing such mixtures.

Description

FUNGICIDAL MIXTURES BASED ON A TRIAZOLOPYRIMIDINE DERIVATE AND AZOLES

5 Description

The present invention relates to fungicidal mixtures comprising as active components

10 A) the triazolopyrimidine derivative of the formula I,

20 and

B) an azole derivative or its salts or adducts selected from

25 (1) bromuconazoles of the formula II

and

(2) difenoconazoles of formula III

and

45 (3) Diniconazoles of Formula IV

and

(4) Fenbuconazole of Formula V

and

(5) Fluquinconazoles of Formula VI

and

(6) Flusilazoles of Formula VII

and

(7) Hexaconazoles of Formula VIII

and (8) Prochloraz of Formula IX

and

(9) Tetraconazoles of formula X

and

(10) Triflumizoles of Formula XI

and

(11) Flutriafol of Formula XII

and

(12) Myclobutanil of Formula XIII

and

(13) Penconazole of the formula XIV

and

[14) Simeconazoles of the formula XV

and

(15) Ipconazoles of formula XVI

and

(16) Triticonazoles of Formula XVII

and

(17) Prothioconazoles of Formula XVIII

XVIII in a synergistically effective amount.

The invention also relates to a method for controlling harmful fungi with mixtures of the compound I with at least one of the compounds II to XVIII and the use of the compound I with at least one of the compounds II to XVIII for the production of such mixtures and agents which contain these mixtures.

The compound of formula I, 5-chloro-7- (4-methyl-piperidin-l-yl) 6- (2, 4, 6-trifluorophenyl) - [1,2,4] triazolo [1, 5- a] pyrimidine, its preparation and its action against harmful fungi is known from the literature (WO-A 98/46607). Mixtures of triazolopyrimidine derivatives with other active ingredients are generally known from EP-A 988 790 and US 6,268,371.

The synergistic mixtures of triazolopyrimidines described in EP-A 988 790 are described as being fungicidally active against various diseases of cereals, fruits and vegetables, in particular mildew on wheat and barley or gray mold on apples.

The azole derivatives II to XVIII, their production and their action against Sadhad fungi are known per se:

Bromuconazole (II), 1- [4-bromo-2- (2,4-dichlorophenyl) tetrahydrofuran-2-ylmethyl] -lH- [1,2,2] triazole: Proc. Br. Crop Prot. Conf. - Pests Dis., 5-6, 439 (1990);

Difenoconazole (III), 1- {2- [2-chloro-4- (4-chlorophenoxy) phenyl] -

4-methyl- [1,3] dioxolan-2-ylmethyl} -1H- [1,2,4] triazole: GB-A

2,098,607;

Diniconazole (IV), 1- (2, 4-dichlorophenyl) -4, 4-dimethyl-2- [1,2,4] triazol-1-yl-pent-1-en-3-ol: CAS RM [83657-24-3];

Fenbuconazole (V), 3- (4-chlorophenyl) -2-phenyl-2- [1, 2, 4] triazole-

1-yl-propionitrile: EP-A 251 775;

Fluquinconazole (VI), 3- (2,4-dichlorophenyl) -6-fluoro-2- [1,2,4] triazol-1-yl-3H-guinazolin-4-one: Proc. Br. Crop Prot. Conf. -Pests Dis. , 5-3, 411 (1992);

Flusilazole (VII), l- {[bis- (4-fluoro-phenyl) -methylsilanyl] - methyl} -lH- [1,2,4] triazole: Proc. Br. Crop Prot. Conf.-Pests Dis.,

1, 413 (1984);

Hexaconazole (VIII), 2- (2, 4-dichlorophenyl) -1- [1, 2,] triazol-1-yl-hexan-2-ol: CAS RN [79983-71-4];

Prochloraz (IX), imidazole-1-carboxylic acid propyl- [2- (2, 4, 6-trichlorophenoxy) ethyl] amide: ÜS-A 3 991 071;

Tetraconazole (X), l- [2- (2, 4-dichlorophenyl) -3- (1, 1,2, 2-tetrafluoroethoxy) propyl] -lH- [1,2, 4] triazole: Proc. Br. Crop Prot. Conf. -Pests Dis., 1, 49 (1988);

Triflumizole (XI), (4-chloro-2-trifluoromethylphenyl) - (2-propoxy-l- [1,2,4] triazol-l-yl-ethylidene) amine: JP-A 79/119 462;

Flutriafol (XII), 1- (4-fluorophenyl) -1- (2-fluorophenyl) -2-

[1,2,4] triazol-l-ylethanol: CAS RN [76674-21-0]; Myclobutanil (XIII), 2- (4-chlorophenyl) -2- [1, 2,4] triazol-1-ylmethylpentanitrile: CAS RN [88671-89-0];

Penconazole (XIV), 1- [2- (2,4-dichlorophenyl) pentyl] -1H-

[1,2,4] triazole: Pesticide Manual, 12th Ed. (2000), page 712;

Simeconazole (XV), 1- (4-fluoro-phenyl) -2- [1, 2, 4] triazol-l-yl-1-trimethylsilanyl-ethanol: The BCPC Conference Pests and Diseases

2000, pp. 557-562; Ipconazole (XVI), 2- (4-chlorobenzyl) -5-isopropyl-l- [1,2,4] triazol-1-ylmethylcyclopentanol: EP-A 267 778;

Triticonazole (XVII), 5- (4-chloro-benzylidene) -2, 2-dimethyl-l- [1,2,4] triazol-1-ylmethyl-cyclopentanol: EP-A 378 953; and prothioconazole (XVIII), 2- [2- (1-chloro-cyclopropyl) -3- (2-chlorophenyl) -2-hydroxypropyl] -2, 4-dihydro- [1,2,4] triazole -3-thio: WO 96/16048.

Fungicidal mixtures are known from EP-A 531 837, EP-A 645 091 and WO 97/06678 which contain one of the azoles II to XVIII as an active ingredient component.

Practical experience in agriculture has shown that the repeated and exclusive use of a single active substance in the control of harmful fungi in many cases leads to the rapid selection of those fungal strains which have developed a natural or adapted resistance to the active substance in question. An effective control of these fungi with the active ingredient in question is then no longer possible.

In order to reduce the risk of selection of resistant fungal strains, mixtures of different active substances are usually used today to combat harmful fungi. Combining active ingredients with different mechanisms of action can ensure long-term control success.

With regard to effective resistance management and an effective control of harmful fungi, the object of the present invention was to provide further means for combating harmful fungi, in particular for certain indications.

Surprisingly, it has now been found that this object is achieved with mixtures which contain the triazolopyrimidine derivative of the formula I as active ingredients and an active ingredient from the group of azoles II to XVIII as a further fungicidally active component.

We have found that this object is achieved by the mixtures defined at the outset. It has also been found that, when the compounds I and the compounds II are used simultaneously or jointly or separately, or when the compound I and one of the compounds II to XVIII are used in succession, harmful fungi can be controlled more effectively than with the individual compounds alone. The mixtures according to the invention act synergistically and are therefore particularly suitable for controlling harmful fungi and in particular powdery mildew in cereals, vegetables, fruit, ornamental plants and vines.

The mixtures according to the invention contain at least one compound of the formula II to XVIII as the azole derivative.

To develop the synergistic effect, a small proportion of triazolopyrimidine derivative of the formula I is already sufficient. Triazolopyrimidine derivative and azole are preferably used in a weight ratio in the range from 100: 1 to 1: 100, preferably 20: 1 to 1:20 , in particular 10: 1 to 1:10.

Because of the basic character of the nitrogen atoms contained in them, the compounds I and II to XVIII 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 as well as glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids with straight-chain or branched alkyl radicals with 1 to 20 carbon atoms), arylsulfonic acids or disulfonic acids such as aromatic res and naphthyl which carry one or two sulfonic acid groups), alkylphosphonic acids (phosphonic acids with straight-chain or branched alkyl radicals having 1 to 20 carbon atoms), arylphosphonic acids or diphosphonic acids (aromatic radicals such as phenyl and naphthyl which carry one or two phosphoric acid radicals), the alkyl or Aryl radicals can carry further substituents, for example p-toluenesulfonic acid, salicylic acid, p-amino salicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid etc.

In particular, the ions of the elements of the first to eighth subgroups, especially chromium, manganese, iron, cobalt, nickel, copper, zinc and in addition to the second main group, especially calcium and magnesium, the third and fourth main group, in particular aluminum, come as metal ions. Tin and lead into consideration. The metals can optionally be present in different valences. Mixtures of the triazolopyrimidine derivative of the formula I with bromuconazole are preferred.

Mixtures of the triazolopyrimidine derivative of the formula I with difenoconazole are preferred.

Mixtures of the triazolopyrimidine derivative of the formula I with diniconazole are preferred.

Mixtures of the triazolopyrimidine derivative of the formula I with fenbuconazole are preferred.

Mixtures of the triazolopyrimidine derivative of the formula I with fluquinconazole are preferred.

Mixtures of the triazolopyrimidine derivative of the formula I with flusilazoles are preferred.

Mixtures of the triazolopyrimidine derivative of the formula I with hexaconazoles are preferred.

Mixtures of the triazolopyrimidine derivative of the formula I with prochloraz are preferred.

Mixtures of the triazolopyrimidine derivative of the formula I with tetraconazoles are preferred.

Mixtures of the triazolopyrimidine derivative of the formula I with triflumizoles are preferred.

Mixtures of the triazolopyrimidine derivative of the formula I with flutriafol are preferred.

Mixtures of the triazolopyrimidine derivative of the formula I with myclobutanil are preferred.

Mixtures of the triazolopyrimidine derivative of the formula I with penconazole are preferred.

Mixtures of the triazolopyrimidine derivative of the formula I with simeconazole are preferred.

Mixtures of the triazolopyrimidine derivative of the formula I with ipconazole are preferred.

Mixtures of the triazolopyrimidine derivative of the formula I with triticonazole are preferred. Mixtures of the triazolopyrimidine derivative of the formula I with prothioconazole are preferred.

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

The mixtures of the compounds I with at least one of the compounds II to XVIII or the compounds I and at least one of the compounds II to XVIII used simultaneously, together or separately are notable for an outstanding action against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Basidiomycetes, Phycomycetes and Deuteromycetes. They are partly systemically effective and can therefore also be used as leaf and soil fungicides.

They are particularly important for combating a large number of fungi on various crops such as cotton, vegetables (eg cucumber, beans, tomatoes, potatoes and squashes), barley, grass, oats, bananas, coffee, corn, fruit plants, rice, rye , Soy, 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 squash plants, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia species on cotton, R izoct , Rice and lawn, üstilago species on cereals and sugar cane, Venturia inaequalis on apples, Bipolaris and Drechs- lera species on cereals, rice and lawn, Septoria nodorum on wheat, Botrytis cinerea on strawberries, vegetables, ornamental plants and vines , Mycosphaerella species on bananas, peanuts and cereals, Pseudocercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Pseudoperonospora species on squashes and hops, Plasmopara viticola on vines, vegetables and AI ternaria species Fruit and Fusarium and Verticillium species.

The mixtures according to the invention can preferably be used for controlling powdery mildew in cereal, vine and vegetable crops and in ornamental plants. In addition, the mixtures according to the invention are also preferably active against harmful fungi from the Oomycetes class, in particular against Phytophthora infestans in potatoes and tomatoes.

The mixtures according to the invention are preferably also suitable for controlling rice pathogens.

Due to the special cultivation conditions of rice plants, there are significantly different requirements for a rice fungicide than for fungicides that are used in cereal or fruit growing. There are serious differences in modern rice cultivation systems: in addition to the spray application common in many countries, the fungicide is applied to the soil directly during or shortly after sowing. The fungicide is absorbed into the plant via the roots and transported in the plant sap in the plant to the parts of the plant to be protected. A high system is therefore essential for rice fungicides. In cereal or fruit growing, on the other hand, the fungicide is usually applied to the leaves or the fruits, so the systemics of the active ingredients play a significantly smaller role in these crops.

Other pathogens are also typical in rice than in cereals or fruit. Pyricularia oryzae, Cochliobolus miyabeanus and Corticium sasakii (syn. Rhizoctonia solani) are the causative agents of the most important diseases of rice plants. Rhizoctonia solani is the only agronomically important pathogen within the Agaricomycetidae subclass. This fungus does not attack the plant via spores like most other fungi, but via a mycelial infection.

For this reason, findings on the fungicidal effects of cereal or fruit growing cannot be transferred to rice crops.

The compound I and at least one of the compounds II to XVIII can be applied simultaneously, that is jointly 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.

The application rates of the mixtures according to the invention, especially in the case of agricultural crop areas, are 5 to 2000 g / ha, preferably 50 to 1500 g / ha, in particular 50 to 750 g / ha, depending on the type of effect desired.

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

If pathogenic fungi are to be combated for plants, the compounds I and at least one of the compounds II to XVIII or their mixtures of the compounds I and at least one of the compounds II to XVIII are applied separately or together by spraying or dusting the seeds, the plants or the soil before or after sowing the plants or before or after the emergence of the plants.

The fungicidal synergistic mixtures according to the invention or the compound I and at least one of the compounds II to XVIII can be used, for example, in the form of directly sprayable solutions, powders and suspensions or in the form of high-strength aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, Pastes, dusts, scattering agents or granules are prepared and used by spraying, atomizing, dusting, scattering or pouring. The form of application depends on the intended use; in any case, it should ensure as fine and uniform a distribution of the mixture according to the invention as possible.

The compounds I and II to XVIII, the mixtures or the corresponding formulations are used in such a way that the harmful fungi, their habitat or the plants, seeds, soils, areas, materials or spaces to be kept free from them are mixed with a fungicidally effective amount of the mixture, or of the compounds I and at least one of the compounds II to XVIII treated separately.

The application can take place before or after the infestation by the harmful fungi.

The formulations are prepared in a known manner, for example 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 liquors and methyl cellulose.

Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylaryl sulfonates, 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 the naphthalene sulfonic acid with phenol and formaldehyde, polyoxyetylenoctylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributylphenylpolyglycol ether, tristerylphenylpolyglycol ether, alkyl arylpolyether alcohols, alcohol- and fatty alcohol ethoxylated ethoxylated ethoxylated alcohol, ethoxylated alcohol ether, ethoxylated alcohol ether, ethoxylated alcohol, ethoxylated alcohol, ethoxylated alcohol, ethoxylated alcohol, ethoxylated alcohol, ethoxylated alcohol and ethoxylated alcohol, , Sorbitol esters, lignite sulfite liquors and methyl cellulose.

Mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, are also used to produce directly sprayable solutions, emulsions, pastes or oil dispersions

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 spreading 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 cereal 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 dispersant 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). When diluted in water, an emulsion results.

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 added with the addition of dispersing and wetting agents and water or an organic Crushed solvent in a stirred ball mill into a fine suspension of active ingredient. 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 are 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 intimately mixed 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 can be used. 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, old dispersions) by adding water. To prepare emulsions, pastes or oldispersions, 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, concentrates consisting of an active substance, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or oil can also be prepared 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.

applications

The synergistic effect of the mixtures according to the invention can be demonstrated by the following experiments:

The active substances were formulated separately or together as a stock solution with 0.25% by weight of active substance in acetone or DMSO. 1% by weight of emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) was added to this solution. The active substances or mixtures were diluted with water in accordance with the stated concentration.

The evaluation is carried out by determining the affected leaf areas in percent. These percentages are converted into efficiencies. Efficiency (W) is determined 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; at an efficiency of 100, the treated plants showed no infection.

The expected efficacies of the active ingredient mixtures were calculated using the Colby formula [R.S. Colby, Weeds 15, 20-22 (1967)] and compared with the observed efficiencies.

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 ay der Efficiency, expressed in% of the untreated control, when using the active ingredient B in the concentration b

Example of use 1 - Protective activity against rice blight caused by Pyricularia oryzae

Leaves of rice seedlings of the "Tai-Nong 67" variety, grown in pots, were sprayed to runoff point with an aqueous suspension in the active compound concentration given below. The following day, the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae. The test plants were then placed in climatic chambers at 22-24 ° C and 95-99% relative humidity for 6 days. The extent of the development of the infestation on the leaves was then determined visually.

Table A - Individual substances

*) Efficiency calculated according to the Colby formula

Example of use 2 - Efficacy against the brown spot disease of the rice caused by Cochliobolus miyabeanus with protective treatment

Leaves of rice seedlings of the "Tai-Nong 67" variety, grown in pots, were sprayed to runoff point with an aqueous suspension in the active compound concentration given below. The following day, the plants were inoculated with an aqueous spore suspension of Cochliobolus miyabeanus. The test plants were then placed in climatic chambers at 22-24 ° C and 95-99% relative humidity for 6 days. The extent of the development of the infestation on the leaves was then determined visually.

Table C - Individual active substances

*) Efficiency calculated according to the Colby formula

Example of use 3 - Efficacy against vine peronospora caused by Plasmopara viticola

Leaves of potted vines were sprayed to runoff point with an aqueous suspension in the active ingredient concentration given below. The following day, the undersides of the leaves were inoculated with an aqueous sporangia suspension of Plasmopara viticola. The vines were then placed for 48 hours in a steam-saturated chamber at 24 ° C and then for 5 days in a greenhouse at temperatures between 20 and 30 ° C. After this time, the plants were again in one for 16 hours in order to accelerate the sporangium carrier outbreak damp chamber. The extent of the development of the infestation on the undersides of the leaves was then determined visually.

Table E - Individual active substances

*) Calculated work gram according to the Colby formula From the results of the tests show that the obser _¬ tete efficiency of the inventive mixtures in all ratios Mi _¬ research is significantly higher than the Colby For _¬ mel predicted.

Claims

23Patentansprüche

Fungicidal mixtures containing as active components

A) the triazolopyrimidine derivative of the formula I,

and

B) an azole derivative or its salts or adducts selected from

(1) Bromuconazoles of formula II

and

(2) difenoconazoles of formula III

and

(3) Diniconazoles of Formula IV

and (4) Fenbuconazole of Formula V

and

(5) Fluquinconazoles of Formula VI

and

(6) Flusilazoles of Formula VII

and

(7) Hexaconazoles of Formula VIII

and

(8) Prochloraz of Formula IX

and (9) Tetraconazoles of formula X

and

(10) Triflumizoles of Formula XI

and

(11) Flutriafol of Formula XII

and

(12) Myclobutanil of Formula XIII

and

(13) Penconazole of the formula XIV

and

(14) Simeconazoles of Formula XV

and

(15) Ipconazoles of formula XVI

and

(16) Triticonazoles of Formula XVII

and

(17) Prothioconazoles of Formula XVIII

XVIII in a synergistically effective amount.

2. Fungicidal mixtures according to claim 1, characterized in that the weight ratio of the triazolopyrimidine of the formula

I to the respective triazole of the formulas II to XVIII is 100: 1 to 1: 100.

3. Fungicidal compositions comprising the fungicidal mixtures according to claims 1 or 2 and a solid or liquid carrier.

4. A method for controlling phytopathogenic harmful fungi, characterized in that the harmful fungi, their habitat or the plants, seeds, soils, areas, materials or spaces to be kept free by them with the triazolopyri-din of formula I according to claim 1 and Azoles of the formula II to XVIII according to claim 1 or the agents according to claim 3 treated.

5. The method according to claim 4, characterized in that the compound of formula I according to claim 1 and at least one compound of formula II to XVIII according to claim 1 at the same time, namely together or separately, or in succession.

6. The method according to claim 4 or 5, characterized in that the fungicidal mixture or the compound of formula I with at least one compound of formula II to XVIII according to claim 1 in an amount of 5 to 2000 g / ha.

7. The method according to any one of claims 4 to 6, wherein harmful fungi from the Oomycetes class are controlled.

8. The method according to any one of claims 4 to 6, wherein rice pathogenic harmful fungi are controlled.

9. Seed containing the mixture according to claims 1 or 2 in an amount of 1 to 1000 g / 100 kg.

10. Use of the compounds I and II to XVIII according to claim 1 for the preparation of a fungicidal composition according to claim 3.