HRP960254A2 - Combinations of active fungicidal agents - Google Patents

Description

The proposed invention relates to new combinations of active substances consisting of the known 8-t-butyl-2-(N-ethyl-N-n-propylamino)-methyl-1,4-dioxaspiro[5,4]decane and two other known derivatives triazoles and are very suitable for controlling fungi.

It is already known that 8-t-butyl-2-(N-ethyl-N-n-propyl-amino)-methyl-1,4-dioxaspiro[5,4]decane, 1-(4-chlorophenyl)-4, 4- dimethyl-3-(1,2,4-triazol-1-yl-methyl)-pentan-3-ol (= tebuconazole) and 2-(2, 4-dichloro-phenyl)-2-(1,2,4 -triazol-1-yl-methyl)-4-n-propyl-1,3-dioxolane (= propiconazole) have fungicidal properties (compare (EP-A 0 281 842, EP-A 0 040 345 and DE-A 2 551 560).

Furthermore, it is also known that mixtures of

- 8-t-butyl-2-(N-ethyl-N-n-propylamino)-methyl-1,4-dioxaspiro[5,4]decane and tebuconazole, or

- 8-t-butyl-2-(N-ethyl-N-n-propylamino)-methyl-1,4-dioxaspiro[5,4]decane and propiconazole, or

- tebuconazole and propiconazole

can be used to control fungi (compare EP-A 0 393 746 and EP-A 0 627 163).

The effectiveness of individual components, as well as the effectiveness of known mixtures of two active substances each, is also good. At very low consumption quantities, the fungicidal option remains desirable in most cases.

It has now been found that new combinations of active substances from

A) 8-t-butyl-2-(N-ethyl-N-n-propylamino)-methyl-1,4-dioxaspiro[5, 4]decane of the formula

[image]

and

B) 1-(4-chloro-phenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)-pentan-3-ol of the formula

[image]

and

C) 2-(2,4-dichloro-phenyl)-2-(1,2,4-triazol-1-yl-methyl)-4-n-propyl-1,3-dioxolane of the formula

[image]

they have very good fungicidal properties.

The fungicidal efficiency of combinations according to the invention of three active substances is surprisingly significantly higher than the efficiency of individual components, that is, the efficiency of previously known mixtures of two active substances each. It is, therefore, about an unpredictable, real synergistic effect, and not just about supplementing efficiency.

Active substances contained in combinations of active substances according to the invention and possible combinations of these components of two active substances each are known (compare EP-A 0 281 842, EP-A 0 040 345, DE-A 2 551 560, EP-A 0 393 796 and EP-A 0 627 163). The active substances of formulas (II) and (III) can also be used in the form of acid addition salts.

When the active substances in the combinations according to the invention are present in specific mass ratios, the synergistic effect is particularly clear. However, the mass ratios of active substances in combinations of active substances can vary over a relatively large range.

In general, 0.1 to 1.5 mass fraction, preferably 0.1 to 1.2 mass fraction of the active substance of formula (II) and 0.1 to 1.5 mass fraction per 1 g mass fraction of the active substance of formula (I) , preferably 0.1 to 1.2 mass fraction of the active substance of formula (III).

The combinations of active substances according to the invention have very good fungicidal properties and can be used to control phytopathogenic fungi, such as Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes, etc.

For example, but without limitation, the causative agents of fungal and bacterial diseases that fall under the main terms listed above are listed:

Xanthomonas species, such as Xanthomonas oryzae;

Pseudomonas species, such as Pseudomonas lachrymans;

Erwinia species, such as Erwinia amylovora;

Pythium species, such as Pythium ultimum;

Phytophthora species, such as Phytophthora infestans;

Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubensis;

species of Plasmopara, such as Plasmopara viticola;

Downy mildew species, such as Downy mildew or P. brassicae;

species of Erysiphe, such as Erysiphe graminis;

Sphaerotheca species, such as Sphaerotheca fuliginea;

Podosphaera species, such as Podosphaera leucotricha;

species of Venturia, such as Venturia inaequalis;

Pyrenophora species, such as Pyrenophora teres or P. graminea;

(form of conidia: Drechslera, Syn: Helminthosporium) ;

Cochliobolus species, such as Cochliobolus sativus;

(form condia: Drechslera, Syn: Helminthosporium) ;

Uromyces species, such as Uromyces appendiculatus, Puccinia species, such as Puccinia recondita;

Tilletia species, such as Tilletia caries;

Ustilago species, such as Ustilago nuda or Ustilago avenae;

Pellicularia species, such as Pellicularia sasakii;

Pyricularia species, such as Pyricularia oryzae;

species of Fusarium, such as Fusarium culmorum;

Botrytis species, such as Botrytis cinerea;

Septoria species, such as Septoria nodorum;

Leptosphaeria species, such as Leptosphaeria nodorum;

Cercospora species, such as Cercospora canescens;

Alternaria species, such as Alternaria brassicae;

Pseudocerosporella species, such as Pseudocerospoella herpotrichoides.

Combinations of active substances according to the invention are particularly suitable for controlling grain diseases such as Pyrenophora teres, Erysiphe graminis, Leptosphaeria nodorum, Rhynchosporium secalis, Septoria tritici, Puccinia spp., Fusarium spp. and Cochliobolus sativus.

Good plant tolerability of combinations of active substances in the concentrations necessary to control plant diseases enables the treatment of aerial parts of plants, plant products and seeds, and soil.

Combinations of active substances can be translated into common formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active substances, the smallest particles encapsulated in polymeric materials and in seed coating materials, further in formulations with fuel attachments, such as smoking cartridges, doses, spirals and the like, and formulations of ULV-cold and warm mist.

These formulations are produced in a known manner, for example by mixing the active substance with an active filler, i.e. with liquid solvents, liquid gases held under pressure and/or with solid carriers, if necessary with the use of surface-active agents, i.e. emulsifiers and/or dispersants and/or foaming agents. In the case of using water as an active filler, for example, organic solvents can also be used as auxiliary solvents. As liquid solvents mainly come into consideration: aromatics such as xylene, toluene, or alkylnaphthalene, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffin, e.g. petroleum fractions, alcohols, such as butanol or glycol and their ethers and esters, ketones, such as acetone, methylethylketone, methylisobutylketone or cyclohexanone, strong polar solvents, such as dimethylformamide and dimethylsulfoxide, and water; by gaseous active fillers in the liquid state or carriers, we mean such liquids that are gaseous at normal temperature, for example propellant gas of aerosols, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; as solid carrier substances come into consideration: eg natural stone flours, such as kaolins, clays, talc, chalk, quartz, aapulgite, montmorillonite or diatomaceous earth and synthetic stone flours, such as highly dispersed silica, aluminum trioxide and silicates; as solid carriers for granules, the following are considered: for example, broken and fractionated natural stone such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules made of inorganic and organic flour and granules made of organic materials such as sawdust, coconut shells, corn cobs and stalks tobacco; as emulsifiers and/or foaming agents come into consideration: eg nonionic and anionic emulsifiers, such as esters of polyoxyethylene-fatty acids, ethers of polyoxyethylene-fatty alcohols, eg alkylaryl-polyglycol-ether, alkylsulfonate, alkylsulfate, arylsulfonate and protein hydrolysates; as dispersants come into consideration: for example, lignin-sulfite waste solutions and methyl-cellulose.

Adhesives such as carboxymethylcellulose, natural and synthetic powdered, granular or latex polymers can be used in the formulations, as well as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalin and lecithin, and synthetic phospholipids. Further additives can be mineral and vegetable oils.

In the formulations, dyes can be used as inorganic pigments, e.g. iron oxide, titanium oxide, ferrocyanine blue and organic dyes, such as alizarin-, azo- and metalphthalocyanine dyes and elements that may be found in food in traces such as iron, manganese, boron salts , copper, cobalt, molybdenum and zinc.

Formulations generally contain between 0.1 and 95% by weight of active substance, preferably between 0.5 and 90%.

Combinations of active substances according to the invention can be present in formulations in a mixture with other known active substances, such as fungicides, insecticides, acaricides and herbicides, and in mixtures with fertilizers or plant growth regulators.

Combinations of active substances as such can be applied in the form of their formulations or in a form prepared from them for application, as ready-to-use solutions, emulsion concentrates, emulsions, suspensions, dusting powders, soluble powders and granules.

The application is carried out in the usual way, for example by casting, spraying, spraying, coating, dry baths, wet baths, wet baths, mud baths or incrustation.

When processing parts of plants, the concentrations of active substances in the application form can vary widely. They generally range between 1 and 0.0001 wt. %, preferably between 0.5 and 0.001%.

When processing seeds, amounts of active substance from 0.001 to 50 g per kilogram of seed are generally required, preferably 0.01 to 10 g.

In soil treatment, active substance concentrations of 0.00001 to 0.1 mass are required. %, preferably from 0.0001 to 0.02 wt. %, at the point of action.

The good fungicidal effect of the combinations according to the invention can be seen from the following examples. While the individual active substance and also combinations of two active substances each show a weakening of the fungicidal effect, combinations of three active substances show an effect that exceeds the simple addition of the effect, and is also above the effect of known combinations with a synergistic effect.

A synergistic effect with fungicides always exists when the fungicidal effect of combinations of active substances is greater than the sum of the effects of individual applied active substances.

The use of combinations according to the invention follows from the following examples.

Example 1

Testing for Leptosphaeria nodorum (wheat) / protection

For the production of a purposeful preparation of the active substance, the usual commercial formulations of the active substance are diluted with water to the desired concentration.

To test the protective effectiveness, young plants are sprayed with the preparation of the active substance with the specified consumption amount.

After drying the sprayed coating, the plants are sprinkled with a suspension of Leptosphaeria nodorum spores. The plants are kept in an incubation chamber for 48 hours at 20°C and 100% relative humidity.

The plants are placed in a growth room at a temperature of approx. 15°C and approx. 80% relative air humidity.

10 days after inoculation, evaluation is done. Here, 0% means a degree of efficiency that corresponds to the control plants, while a degree of efficiency of 100% means that no infection was observed.

Active substances, applied amounts and test results are shown in the following table.

Table 1 Testing for Leptosphaeria nodorum (wheat) / protection

[image]

Example 2

Testing with Fusarium nivale (var. nivale) (wheat) protective

For the production of a purposeful preparation of the active substance, the finished formulation of the active substance is diluted with water to the desired concentration.

To test the protective effectiveness, young plants are sprayed with the preparation of the active substance in the stated consumption amount.

After drying the sprayed coating, the plants are sprinkled with a suspension of conidia of Fusarium nivale var. nivale.

The plants are kept in a growth chamber under a light-permeable incubation cover at a temperature of approx. 15°C and approx. 100% relative air humidity.

4 days after inoculation, evaluation is done. Here, 0% means a degree of efficiency that corresponds to the control plants, while a degree of efficiency of 100% means that no infection was observed.

Active substances, applied amounts and test results are shown in the following table.

Table 2

Testing for Fusarlum nivale (var. nivale) (wheat) / protection

[image]

Claims (5)

1. Fungicidal agent, characterized by the fact that it contains a combination of active substances consisting of A) 8-t-butyl-2-(N-ethyl-N-n-propylamino)-methyl-1,4-dioxaspiro[5, 4]decane formulas [image] and B) 1-(4-chloro-phenyl)-4,4-dimethyl-3-(1, 2, 4-triazol-1-yl-methyl)-pentan-3-ol of the formula [image] C) 2-(2, 4-dichloro-phenyl)-2-(1,2,4-triazol-1-yl-methyl)-4-n-propyl-1,3-dioxolane of the formula [image] 2. Means according to claim 1, characterized by the fact that in combinations of active substances, the ratio of the active substance of the formula (I) to the active substance of the formula (II) is between 1:0.1 and 1:1.5, and to the active substance of the formula ( III) is between 1:0.1 and 1:1.5. 3. Method for combating fungi, indicated by the fact that combinations of active substances according to claim 1 are allowed to act on fungi and/or their living space. 4. The use of combinations of active substances according to claim 1, characterized in that they are used to combat fungi. 5. Process for the production of fungicidal agents, characterized in that the combinations of active substances according to claim 1 are mixed with active fillers and/or surfactants.